Applied Clay Science 20 (2002) 295 – 300

www.elsevier.com/locate/clay

Adsorption of methylene blue on kaolinite

Dipa Ghosh, Krishna G. Bhattacharyya *
Department of Chemistry, Gauhati University, Guwahati 781014, Assam, India
Received 29 May 2000; received in revised form 1 February 2001; received in revised form 2 July 2001; accepted 9 July 2001

Abstract

Methylene blue was adsorbed on kaolin from a local deposit. The raw kaolin itself was a relatively good adsorbent. The
adsorption capacity was improved by purification and by treatment with NaOH solution. Calcination of the kaolin reduced the
adsorption capacity. The adsorption data could be fitted by the Freundlich and Langmuir equations. Also, the thermodynamic
parameters such as DH0, DS0 and DG0 were determined. D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Kaolinite; Adsorption; Methylene blue

1. Introduction In industrial water pollution, the colour produced

Kaolinite is found as a common constituent of soils
and sediments. When different types of pollutants in
domestic sewage, industrial effluents, sludge and
other solid wastes are dumped on the earth surface,
the soil particles including clay minerals can interact
with the pollutants. The clay minerals in soil may
therefore play a role in scavenging pollutants from the
environment. Kaolinite has a low CEC of the order of
3 to 15 meq/100 g and therefore it is not expected to
be an ion-exchanger of high order. The small number
of exchange sites is located on the surface of kaolinite
and it has no interlayer exchange sites (Raymahashay,
1987). Nevertheless, the small CEC and the adsorp-
tion properties may play an effective role in scaveng-
ing inorganic and organic pollutants from water.
*
Corresponding author. Fax: +91-361-570133.
E-mail address: krishna111@sancharnet.in
(K.G. Bhattacharyya).
by minute amounts of organic dyes in water is
considered very important because, besides having
possible harmful effects, the colour in water is aes-
thetically unpleasant. The clays in soil can act as a
natural scavenger in removing colour from the con-
taminated water. In the present study, aqueous solu-
tions of a basic dye, methylene blue, were used as a
model compound in an attempt to use kaolinite as an
adsorbent.
Although not strongly hazardous, methylene blue
can have various harmful effects. On inhalation, it can
give rise to short periods of rapid or difficult breathing
while ingestion through the mouth produces a burning
sensation and may cause nausea, vomiting, diarrhea,
and gastritis. Accidental large dose creates abdominal
and chest pain, severe headache, profuse sweating,
mental confusion, painful micturation, and methemo-
globinemia.
The adsorption of methylene blue on clay minerals
is likely to be dominated by ion-exchange processes.
In the present work, the influence of (a) purification

0169-1317/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 1 3 1 7 ( 0 1 ) 0 0 0 8 1 - 3
296 D. Ghosh, K.G. Bhattacharyya / Applied Clay Science 20 (2002) 295–300
and calcination, (b) the adsorbent dose, (c) concen-
tration of methylene blue, (d) pH of the medium and
(e) temperature of adsorption is investigated. The
effect of treating the kaolin with an aqueous NaOH
solution is also studied.
2. Experimental
2.1. Materials
The kaolin, in bright white lumps, was collected
from Silonijan in the district of Karbi Anglong in
Assam (India). After collection, stones and other
heavy particles were removed from the samples,
which were then crushed, ground and sieved through
a 230-mesh sieve to remove the larger non-clay
fractions for obtaining raw kaolin. A part of the
raw kaolin was kept suspended in double distilled
water in a 1-l beaker for several hours and then the
mixture was stirred with the addition of a small
amount of 30% hydrogen peroxide solution to
remove organic substances till all effervescence
ceased. The mixture was kept standing overnight
and then, after decanting the clear liquid from the
top, more water was added, stirred, and allowed to
settle down for 3 –4 h. The clear liquid at the top was
again decanted and the process was repeated several
times to get rid of excess hydrogen peroxide solution.
Finally, after adding more water, the mixture was
agitated vigorously for some time and the suspended
kaolin was taken in several wide glass plates, which
were kept in an air oven at around 343 K for slow
evaporation to dryness for obtaining pure kaolin
(Moore and Reynolds, 1989). XRD and IR measure-
ments showed the pure kaolin to be of very high
purity with only trace amounts of feldspar. The pure
kaolin was found to be similar to a kaolin sample
(KGa-1b) obtained from the University of Missouri-
Columbia, Source Clay Minerals Repository, Colum-
bia.
Samples of both raw and pure kaolin were calcined
at 770 K for 6 h. Amounts of 6 g of raw and pure
kaolin were also shaken with 100 ml 1 M NaOH for 4
h, left overnight, filtered, and washed with water. The
residue was dried at 350 K.
Methylene blue (microscopic grade, Glaxo India,
Mumbai) was used without any further purification.
2.2. Adsorption studies
Adsorption of methylene blue was carried out in a
batch process by varying kaolin dose, adsorptive
concentration, pH of medium and temperature. A
weighed sample of kaolin was mixed with 25 ml
methylene blue solution of known concentration.
The mixture, in a 100-ml conical flask, was shaken
in the water bath of a thermostat at a particular
temperature for 3 h. In all cases, adsorption equili-
brium was reached within
2 h. If necessary, the pH
was adjusted by adding a few drops of dilute NaOH or
HCl before shaking. The mixture was allowed to settle
and was centrifuged. The methylene blue concentra-
tion in the supernatant was determined with a spec-
trophotometer (Hitachi model 3210).
2.3. Adsorption isotherms
The adsorption data from the experiments were
fitted with:
ðaÞ Freundlich Isotherm : x=m ¼ KCen ð1Þ
where x/m is the amount of methylene blue adsorbed
on the unit mass of the adsorbent, Ce is the equili-
brium adsorbate concentration in aqueous phase, n
and K are the Freundlich’s constants.
ðbÞ Langmuir Isotherm : Ce =ðx=mÞ
¼ ð1=abÞ þ ð1=bÞCe ð2Þ
where a and b are the Langmuir constants.
The constants were obtained from the plots of the
linearized equations. Another factor, RL, which is
considered as a more reliable indicator of adsorption
(Vermeulan et al., 1966; McConvey and McKay,
1985) was computed from:
RL ¼ 1=ð1 þ aCÞ ð3Þ
where a is Langmuir’s constant and C is any
adsorbate concentration at which the adsorption is
carried out. Favourable adsorption is indicated by
0 < RL < 1.
2.4. Thermodynamic parameters
The thermodynamic parameters of the adsorption
process are obtained from experiments at various
 D. Ghosh, K.G. Bhattacharyya / Applied Clay Science 20 (2002) 295–300 297

The cation exchange capacity (CEC) of the kaolins

was estimated by the conventional BaCl2 method and
was found to be 2.62 (Cl), 2.85 (C2), 1.94 (C3), 3.08
(C4), 2.17 (C5) and 2.42 (C6) meq/100 g. The pure
kaolin and its calcined sample have higher CEC
compared to the other samples. Calcination improved
the CEC of the pure kaolin while that of the raw
kaolin decreased. The treatment with NaOH decreased
the CEC of the raw and pure kaolin.

3.1. Effect of adsorbent and adsorptive doses

The adsorption of methylene blue at a fixed kaolin

Fig. 1. Adsorption of methylene blue as a function of the initial
methylene blue concentration. Contact time 3 h, kaolin dose 0.8 g/l,
temperature 300 K.
temperatures using the following equations (Khan et
al., 1995):
ðaÞ logKd ¼ DS 0 =ð2:303RÞ  DH 0 =ð2:303RT Þ ð4Þ
dose of 0.8 g/l at 300 K is shown in Fig. 1. The
sample C6 showed the maximum adsorption. The
adsorption decreased in the order C 6 > C5 > C2 >
C1 > C4 > C3. The raw kaolin (C1) showed a con-
siderable adsorption, which was reduced after calci-
nation. A similar influence was evident for the pure
kaolin. Treatment with NaOH increased the adsorp-
tion. The NaOH-treated pure kaolin (C6) adsorbed

ðbÞ DG0 ¼ DH 0  T DS 0 ð5Þ

ðcÞ Kd ¼ ðx=mÞ=ðy=uÞ ð6Þ

where Kd is the distribution coefficient for the adsorp-

tive and is equal to the ratio of the amount adsorbed
(x/m in mg/g) to the adsorptive concentration ( y/u in
mg/dm3). The values of DH 0 and DS 0 were deter-
mined from the slope and intercept of the linear plot of
log Kd vs. 1/T.

3. Results and discussion

In all adsorption experiments, six different adsorb-

ents were used:

Cl—raw kaolin,
C2—pure kaolin,
C3—calcined raw kaolin,
C4—calcined pure kaolin, Fig. 2. Variation of the methylene blue adsorption with pH. Contact
C5—NaOH-treated raw kaolin, and time 3 h, initial methylene blue concentration 15 mg/l, kaolin dose
C6—NaOH-treated pure kaolin. 0.8 g/l.
298 D. Ghosh, K.G. Bhattacharyya / Applied Clay Science 20 (2002) 295–300

3.2. Effect of pH

The methylene blue adsorption showed a mini-

mum around pH
4 (Fig. 2). The increased adsorp-
tion at basic conditions may be related to preference
of the dye cations for basic sites. In aqueous
medium, the exchangeable alkali and other metal
cations on the surface and in the interlayer region
of the clay undergo hydration creating a hydrophilic
environment (Lawrence et al., 1998). Increasing the
pH of the adsorbing medium modifies the clay
mineral surface and this might be responsible for
the gradually increasing uptake of methylene blue at
pH values above 4.0. Raymahashay (1987) in his
comparative study of methylene blue adsorption on
kaolin and some other adsorbents also found that the
uptake of the dye increased with increasing pH. This
is normally attributed to enhanced association of the
dye cations, produced by the dissociation of meth-
ylene blue, with the negatively charged kaolin sur-

Fig. 3. Freundlich plots for the adsorption of methylene blue at

room temperature.

nearly 100% methylene blue from a 12-ppm solu-

tion.
The amount of the dye adsorbed showed a con-
tinuous decrease with an increase in the doses of
kaolin for all the six adsorbents. This is because the
equilibrium concentration of the dye decreased with
increasing amount of kaolin such that amount
adsorbed diminished.
The above results indicate that the raw kaolin
showed a substantial methylene blue adsorption.
Higher amounts were adsorbed by the pure kaolin
with a further enhancement in adsorption if this kaolin
was treated with NaOH. The purification of the raw
kaolin by treating with hydrogen peroxide solution
(for removing organic matter) must have resulted in
removal of non-clay matter and in generation of some
basic or anionic sites for binding methylene blue
cations. The treatment with NaOH creates additional
which improve the adsorption. Calcination of the Fig. 4. Langmuir plots for the adsorption of methylene blue at room
samples apparently removed some active sites. temperature.
 D. Ghosh, K.G. Bhattacharyya / Applied Clay Science 20 (2002) 295–300 299

Table 1
Adsorption constants for methylene blue adsorption on kaolins at room temperature
Adsorbents Freundlich constants Langmuir constants
n K a b RL
(dm3 g  1) (dm3 g  1) (mg g  1)
C1 0.151 14.85 27.49 13.99 0.0021
C2 0.070 16.39 91.87 15.55 0.0006
C3 0.075 6.57 13.44 7.59 0.0042
C4 0.061 9.01 56.31 8.88 0.0010
C5 0.047 17.04 204.00 16.34 0.0028
C6 0.098 23.05 122.01 20.49 0.0005

face at higher and higher pH (Singh and Srivastava,
1999). However, the tendency for increasing adsorp-
tion at pH values below 4.0 is difficult to explain,
but a similar result was earlier observed by workers
for adsorption of some other dyes on kaolin (Ganji-
doust et al., 1995).
3.3. Adsorption isotherms
Methylene blue adsorption on the kaolins can be
described by the Freundlich and also Langmuir equa-
tions (Figs. 3 and 4, Table 1). The Freundlich expo-
nent n between 0.047 and 0.151 indicates favourable
adsorption for which 0 < n < 1. The Freundlich con-
stant K is appreciable for all the six adsorbents in
general agreement with strong adsorption. The NaOH-
treated pure kaolin has the largest value of K followed
by the NaOH-treated raw kaolin. The calcined sample
has the lowest K-value.
The values of Langmuir constant b is in the order
of C6 > C5 > C2 > C1 > C4 > C3 which is highest for the
NaOH-treated pure kaolin and lowest for the calcined
sample. The values of the Langmuir constant a also
reflect an almost similar trend. The RL-values between
0.0005 and 0.0042 (Table 1) show favourable adsorp-
tion of methylene blue on kaolin.

Fig. 5. Log Kd vs. 1/T for six different doses of raw kaolin.
300 D. Ghosh, K.G. Bhattacharyya / Applied Clay Science 20 (2002) 295–300

Table 2 4. Conclusion
Thermodynamic parameters for adsorption of methylene blue on
kaolins
The adsorption experiments reveal that kaolinite
Adsorbent DH 0 DS 0  DG 0
clay may be quite effective in removing a basic dye
(kJ mol  1) (J mol  1 K  1) (kJ mol  1)
like methylene blue in relatively low concentrations
C1 9.40 78.39 14.94
from the aqueous medium. Although the experiments
C2 7.54 73.53 15.29
C3 13.53 88.16 13.85 have been done with the raw kaolin and five modified
C4 11.84 84.32 14.34 forms, the raw kaolin itself has a relatively large
C5 7.92 74.99 15.37 adsorption capacity.
C6 6.03 69.69 15.61

3.4. Thermodynamic parameters
A typical log Kd vs. 1/T plot is shown in Fig. 5.
The values demonstrate a spontaneous and favourable
adsorption process. The standard enthalpy change
(DH0) for the adsorption process is positive indicating
that the process is endothermic in nature. The endo-
thermic nature of adsorption of methylene blue was
earlier observed by Mall and Upadhyay (1995,1998)
with boiler bottom ash and fly ash as the adsorbents,
and also by De and Basu (1999) with a sawdust-based
adsorbent. Singh and Srivastava (1999) obtained pos-
itive DH and DS, and negative DG values for
adsorption of methylene blue and a few other basic
dyes on plant leaves in agreement with the present
work.
The values of standard entropy change (DS0) are
not very large and indicate an increase due to adsorp-
tion. Normally, adsorption of gases leads to a decrease
in entropy due to orderly arrangement of the gas
molecules on a solid surface. However, the same
may not be true for the complicated system of
adsorption from solution on a non-uniform kaolin
surface. Entropy increase was also observed by other
workers as is pointed out above. The negative values
of standard Gibbs energy change (DG0) in all the
cases are indicative of the spontaneous nature of the
interaction without requiring large activation energies
of adsorption. Each of the thermodynamic parameters
is in a narrow range of values for all the six clay
adsorbents and therefore, it may be concluded that the
thermodynamic processes involved in the clay –meth-
ylene blue interaction for all the adsorbents are more
or less uniform in nature (Table 2).
Acknowledgements
The authors are grateful to the Assam Science,
Technology and Environment Council (ASTEC) for
providing a financial grant for this work.
References
De, D.S., Basu, J.K., 1999. Adsorption of methylene blue on to a
low cost adsorbent developed from sawdust. Indian J. Environ.
Prot. 19, 416 – 421.
Ganjidoust, H., Samadian, M., Deyhoal, F., 1995. Removal of dyes
by sorption on soil from textile industries. Proc. of Third Intl.
Conf. on Appropriate Waste Management Technology for De-
veloping Countries, NEERI, Nagpur, pp. 523 – 530.
Khan, S.A., Rehman, R., Khan, M.A., 1995. Adsorption of Cr (III),
Cr (VI) and Ag (I) on bentonite. Waste Manage. 15, 271 – 282.
Lawrence, M.A.M., Kukkadapu, R.K., Boyd, S.A., 1998. Adsorp-
tion of phenol and chlorinated phenols from aqueous solution
by tetramethylammonium- and tetramethylphosphonium-ex-
changed montmorillonite. Appl. Clay Sci. 13, 13 – 20.
Mall, I.D., Upadhyay, S.N., 1995. Removal of basic dyes from
wastewater using boiler bottom ash. Indian J. Environ. Health
37, 1 – 10.
Mall, I.D., Upadhyay, S.N., 1998. Studies on treatment of basic
dyes bearing wastewater by adsorption treatment using fly
ash. Indian J. Environ. Health 40, 177 – 188.
McConvey, I.F., McKay, G., 1985. Chem. Eng. Process. 19,
267 – 275.
Moore, D.M., Reynolds Jr., R.C. 1989. X-ray Diffraction and the
Identification and Analysis of Clay Minerals. Oxford Univ.
Press, Oxford, pp. 179 – 201.
Raymahashay, B.C., 1987. A comparative study of clay minerals for
pollution control. J. Geol. Soc. India 30, 408 – 413.
Singh, D.K., Srivastava, B., 1999. Removal of basic dyes from
aqueous solutions by chemically treated Psidium Guyava leaves.
Indian J. Environ. Health 41, 333 – 345.
Vermeulan, T.H., Hall, K.R., Eggleton, L.C., Acrivos, A., 1966. Ind.
Eng. Chem. Fundam. 5, 212 – 223.