Desalination 265 (2011) 159–168

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Adsorption thermodynamics, kinetics and isosteric heat of adsorption of malachite

green onto chemically modified rice husk
Shamik Chowdhury, Rahul Mishra, Papita Saha ⁎, Praveen Kushwaha
Biotechnology Department, National Institute of Technology-Durgapur, Mahatma Gandhi Avenue, Durgapur (WB) - 713209, India

a r t i c l e i n f o a b s t r a c t

Article history: Rice husk treated with NaOH was tested as a low cost adsorbent for the removal of malachite green from
Received 12 March 2010 aqueous solution in batch adsorption procedure. The adsorption experiments were carried out as a function
Received in revised form 17 July 2010 of solution pH, initial dye concentration, contact time and temperature. The adsorption was found to be
Accepted 26 July 2010
strongly dependent on pH of the medium. The Freundlich isotherm model showed good fit to the
Available online 25 August 2010
equilibrium adsorption data. The mean free energy (E) estimated from the Dubinin–Radushkevich model
indicated that the main mechanism governing the sorption process was chemical ion-exchange. The kinetics
Keywords:
Rice husk
of adsorption followed the pseudo-second-order model and the rate constant increased with increase in
Malachite green temperature indicating endothermic nature of adsorption. The Arrhenius and Eyring equations were used to
Isotherm obtain the activation parameters such as activation energy (Ea), and enthalpy (ΔH#), entropy (ΔS#) and free
Kinetics energy (ΔG#) of activation for the adsorption system. Thermodynamic studies suggested the spontaneous
Thermodynamics and endothermic nature of adsorption of malachite green by treated rice husk. The isosteric heat of
Isosteric heat of adsorption adsorption (ΔHX) was also determined from the equilibrium information using the Clausius–Clapeyron
equation. ΔHX increased with increase in surface loading indicating some lateral interactions between the
adsorbed dye molecules.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction have a tendency to chelate metal ions which result in micro-toxicity to

fish and other organisms [9].
Synthetic dyes are widely used in various industries such as textile, Malachite green (MG), an N-methyl diaminotriphenylmethane
leather, paper, printing, food, cosmetics, paint, pigments, petroleum, dye, is the most widely used for coloring purpose among all other dyes
solvent, rubber, plastic, pesticide, wood preserving chemicals and of its category [10]. It is an extensively used biocide in the aquaculture
pharmaceutical industry [1,2]. Over 10,000 of different commercial industry world-wide. It is also used as a food coloring agent, food
dyes and pigments exist and more than 7 × 105 tonnes are produced additive, a medical disinfectant and anthelminthic as well as a dye in
annually worldwide [3]. Approximately 12% of synthetic dyes are lost silk, wool, jute, leather, cotton, paper and acrylic industries [11–13].
during manufacturing and processing operations and 20% of these lost However there are several reports describing its hazardous and
dyes enter the industrial wastewaters [4]. Textile industries consume carcinogenic effects [14]. It is known to be highly cytotoxic and
two thirds of the dyes manufactured. During textile processing, up to carcinogenic to mammalian cells and acts as a liver tumor promoter.
50% of the dyes are lost after the dyeing process and about 10–15% of In humans, it may cause irritation to the respiratory tract if inhaled
them are discharged in the effluents [5]. The textile manufacturing and causes irritation to the gastrointestinal tract upon ingestion.
industry alone discharges about 146,000 tonnes of dyes per year along Contact to malachite green with skin causes irritation with redness
with its wastewater which ultimately finds its way into the and pain; upon contact with eye will lead to permanent injury of
environment [6]. Generally the wastewater contains dye concentra- human eyes. It also affects the aquatic life and causes detrimental
tions ranging from 10 to 200 mg L− 1 [7]. The discharge of dye effects in liver, gill, kidney, intestine, gonads and pituitary gonado-
containing effluents into the natural water bodies can pose hazardous trophic cells [15,16]. Therefore, the treatment of effluent containing
effects on the living systems because of carcinogenic, mutagenic, such dye is of interest due to its harmful impacts on receiving waters.
allergenic and toxic nature of dyes [8]. Dyes impede light penetration, The disposal of dye wastewater with proper treatment is a big
retard photosynthetic activity, inhibit the growth of biota and also challenge. This is mainly because synthetic dyes used in industries are
designed to resist fading upon exposure to sweat, heat, light, water,
many chemicals including oxidizing agents, and microbial attacks
[17]. The traditional methods for color removal include reverse
⁎ Corresponding author. Tel.: +91 9903739855; fax: +91 3432547375. osmosis, electrodialysis, ultrafiltration, ion-exchange, chemical pre-
E-mail address: [email protected] (P. Saha). cipitation, etc. However, all these methods have disadvantages like

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.07.047
160 S. Chowdhury et al. / Desalination 265 (2011) 159–168

incomplete removal, high reagent and energy generation of toxic

sludge or other waste products that require careful disposal, high
capital and operating costs, labor intensive, etc. In this light,
adsorption has emerged as an efficient and cost-effective alternative
to conventional contaminated water treatment facilities. It is defined
as a process wherein a material is concentrated at a solid surface from
its liquid or gaseous surroundings [3]. Adsorption separation in the
environmental engineering is now an aesthetic attention and
consideration abroad the nations, owning to its low initial cost,
simplicity of design, ease of operation, insensitivity to toxic sub-
stances and complete removal of pollutants even from dilute solutions
[18]. A large variety of natural materials or the wastes/by-products of
industries has been employed as inexpensive adsorbents for dye
removal [3]. The waste materials seem to be viable option for dye
Fig. 1. Structure of malachite green.
removal because of their economic and eco-friendly traits, availability
in abundance, low cost, regeneration of the biosorbent and the
possibility of dye recovery. In this connection, special attention have Stock solution (500 mg L− 1) was prepared by dissolving accurately
been given to agricultural wastes like orange peel, banana pith, weighed quantity of the dye in double-distilled water. Experimental
banana peel, plum kernels, apple pomace, wheat straw, sawdust, coir dye solution of different concentrations was prepared by diluting the
pith, sugarcane bagasse, tea leaves, bamboo dust, etc [3]. stock solution with suitable volume of double-distilled water.
In India, rice husk is an easily available agricultural waste material,
produced in large quantities as a by-product of rice milling and create 2.2. Preparation of adsorbent
potential environmental problems. The annual generation of rice husk
has been estimated to be 18–22 million tonnes [19]. Rice husk Rice husk used was obtained from a nearby rice mill of Durgapur,
possesses a granular structure, is insoluble in water, has chemical West Bengal, India. It was washed repeatedly with double-distilled
stability, high mechanical strength and accounts for about 20% of the water to remove dust and soluble impurities, and this was followed by
whole rice. It consists of about 32% cellulose, 21% hemicelluloses, 21% drying at 343 K for 3 h. The dried rice husk was then suspended in 5%
lignin, 20% silica and 3% crude protein [20,21]. It also contains sodium hydroxide (NaOH) solution and the suspension was auto-
abundant floristic fiber, and some functional groups such as carboxyl, claved at 10 psi for 15 min. The alkali solution was filtered off, and the
hydroxyl and amidogen, etc, representing a favorable characteristic of rice husk was washed thoroughly with distilled water until the rice
rice husk to be a potential adsorbent material [19]. Silica present on husk gave no color and the pH of the wash was close to neutral. The
the outer surface of rice husks in the form of silicon-cellulose treated rice husk was then dried at 343 K for 6 h. After drying, the
membrane acts as a natural protective layer against termites and adsorbent was stored in sealed glass containers. The same adsorbent
other microbial attack on the paddy. This component is however was used in all the experiments.
responsible for insufficient binding between accessible functional
groups on rice husks’ surfaces and various adsorbate ions/molecules. 2.3. Scanning electron microscope (SEM) analysis
The inner surface of rice husk is smooth and may contain wax and
natural fats that provide good shelter for the grain but the presence of In order to characterize the surface structure and morphology of
these impurities on the inner surfaces of rice husks also affects the untreated and treated rice husk and treated rice husk after adsorption
adsorption properties of rice husk chemically and physically [21]. of MG, SEM analysis was carried out using a scanning electron
Therefore, removal of silica and other surface impurities can be microscope (Model Hitachi S-3000N) at an electron acceleration
expected to improve the adsorption properties of rice husk. Chemical voltage of 20 kV. Prior to scanning, the samples were coated with a
modification of rice husk surface is thus necessary to upgrade or thin layer of gold using a sputter coater to make them conductive.
improve the adsorption properties. Alkali treatment of rice husk with
sodium hydroxide (NaOH) has been demonstrated to improve the 2.4. Batch adsorption experiments
adsorption properties [21]. NaOH removes natural fats, waxes and low
molecular weight lignin compounds from the rice husk surface thus The adsorption of MG on alkali treated rice husk was investigated
revealing chemically reactive functional groups like –OH. The removal in batch mode sorption equilibrium experiments. All batch experi-
of the surface impurities also improves the surface roughness of the ments were carried out in 250 mL glass-stoppered, Erlenmeyer flasks
fibers or particles thus opening more hydroxyl groups and other containing a fixed amount of adsorbent with 100 mL dye solution at a
reactive functional groups on the surface. The aim of the present study known initial concentration. The flasks were agitated at a constant
was to investigate and explore the possibility of using alkali treated speed of 200 rpm for 2 h in an incubator shaker (Model Innova 42,
rice husk for adsorption of MG from aqueous solutions. The study New Brunswick Scientific, Canada) at 303 K. The influence of pH (2.0,
includes an evaluation of the effects of various operational parameters 3.0, 4.0, 6.0, 7.0, 9.0), contact time (10, 30, 45, 60, 90, 120 min), initial
such as initial dye concentration, contact time, temperature and pH on dye concentration (10, 20, 50, 100 mg L− 1), and temperature (298,
the dye adsorption process. The adsorption kinetic models, equilib- 303, 303, 313 K) were evaluated during the present study. Samples
rium isotherm models and thermodynamic parameters related with were collected from the flasks at predetermined time intervals for
the process were also performed and reported. analyzing the residual dye concentration in the solution. The residual
amount of dye in each flask was investigated using UV/VIS
2. Materials and methods spectrophotometer (Model Hitachi-2800). The amount of dye
adsorbed per unit adsorbent (mg dye per g adsorbent) was calculated
2.1. Adsorbate according to a mass balance on the dye concentration using Eq. (1):

Malachite green used in this study was of commercial quality (CI

42000, FW: 365, MF: C23H25N2Cl, λ max: 618 nm) and was used ðCi −Ce ÞV
qe = ð1Þ
without further purification. The chemical structure is shown in Fig. 1. m
 S. Chowdhury et al. / Desalination 265 (2011) 159–168 161

where Ci is the initial dye concentration (mg L− 1), Ce is the are large enough to allow the dye molecules to penetrate into the
equilibrium dye concentration in solution (mg L−1), V is the volume lignocellulosic structure and interact therein with the surface groups.
of the solution (L), mis the weight of the treated rice husk in g. All the Fig. 2c illustrates the SEM image of treated rice husk after adsorption
experiments were performed triplicate and the average value from of the dye. It is evident that the surface morphology of the treated rice
results were taken. husk is different before and after adsorption of the dye. The pores were
In an adsorption study, it is necessary to fit the equilibrium completely filled after the adsorption of MG and the pores appear to be
adsorption data using different adsorption isotherm models and prominently swollen. This observation indicates that MG is adsorbed to
kinetic equations in order to analyze and design an adsorption the functional groups present inside the pores. The surface of the treated
process. Therefore, different theoretical models (Table 1) are applied rice husk becomes smooth after adsorption of MG as shown in Fig. 2c.
to experimental data in order to find a model which adequately Smoothness of the surface is due to the adsorption of the dye. It may also
predicts kinetic and isotherm data. The validity of the models was be due to the decrease in surface heterogeneity.
evaluated by the coefficient of determination (r2) and the chi-square
test (χ2) [18].
3.2. Effect of pH

3. Results and discussion The pH of the aqueous solution has been recognized as one of the
most important factors influencing any adsorption process. It
3.1. Scanning electron microscope (SEM) analysis influences not only the surface charge of the adsorbent, the degree
of ionization of the material present in the solution and the
SEM analysis is a useful tool for the analysis of the surface dissociation of functional groups on the active sites of the adsorbent,
morphology of an adsorbent. SEM images of untreated and treated but also the solution dye chemistry [10]. Thus the effect of pH on the
rice husks are shown in Fig. 2a–b. The micrographs in Fig. 2a and b removal efficiency of MG was studied at different pH ranging from 2.0
represent an un-even surface and porous structure of both untreated to 9.0. Results are shown in Fig. 3. It can be seen that adsorption of MG
and treated rice husk. However, as seen in Fig. 2b, the surface was strongly pH-dependent. The equilibrium uptake of dye increased
roughness of rice husk changed significantly after treatment with notably with raising the pH from 2.0 to 4.0. Above these levels, the
alkali. These include wearing of asperities and particle cracking. Pores adsorption capacity did not change significantly up to pH 9.0. Similar
and cavities of various dimensions are also clearly evident on the trend was reported for adsorption of MG on treated ginger waste [38],
surface of treated rice husk. Further, the pores on the surface of the maize cob powder [39], de-oiled soya [40] and coal [41]. The
adsorbent are highly heterogeneous. The heterogeneous pores and maximum sorption capacity takes place at pH 7; % removal of dye
cavities provided a large exposed surface area for the adsorption of was 98.9%. Therefore further experiments were performed at pH 7.
MG. The presence of pores indicates that there was a good possibility MG is a cationic dye, which exists in aqueous solution in the form of
for the dye molecules to be trapped and adsorbed onto the surface of positively charged ions. As a charged species, the degree of its
the adsorbent. The mean size of surface cavities was measured on the adsorption onto the adsorbent surface is primarily influenced by the
image and the average diameter was less than 10 μm. These cavities surface charge on the adsorbent, which in turn is influenced by the

Table 1
Isotherm, kinetic and other equations used in this study.

Model/equation Equation Parameters Ref.

Isotherm models
Ce Ce 1
Langmuir
qe = qm + KL qm qe (mg g−1): equilibrium adsorption capacity [1,23]
qm (mg g− 1): maximum adsorption capacity
KL (L mg−1): Langmuir constant

1 Ce ( mg L−1) : equilibrium adsorbate concentration in solution
Freundlich logqe = logKF + n logCe KF (mg g-1) (L g−1)1/n: Freundlich constant [8,22]
n : Heterogeneity factor
Temkin KT (L g− 1): Temkin adsorption potential [24,25]
qe = BT ln KT + BT ln Ce
BT: Temkin constant
Dubinin–Radushkevich (D–R) β (mmol2/J2): D–R constant [26,27]
ln qe = ln qm − βε2
1 ∈ (Jm mol–1): Polanyi potential
∈ = RT ln (1 + ) R: universal gas constant (8.314 J mol− 1 K− 1)
ce
T(K): temperature

Kinetic models
k1
Pseudo-first-order logðqe −qt Þ = logqe − 2:303 t qt ( mg g− 1): amount of adsorbate adsorbed at time t [28–30]
k1 (min-1): pseudo-first-order rate constant
t 1 1
Pseudo-second-order
qt = k2 q2e
+ qe t k2(g. mg-1 min-1): pseudo-second-order rate constant [30–32]
Elovich α (mg g−1 min−1): initial sorption rate constant [6,33]
β lnðαβÞ
1 1
qt = + β lnt β (g mg-1): desorption constant
Intraparticle-diffusion ki (mg g− 1 min − 0.5): intraparticle diffusion rate constant [30,34]
qt = kit0.5
Liquid film diffusion F: fractional attainment of equilibrium, equal to qt / qe [35]
ln(1 − F) = − kfdt

Activation parameters
Ea
Arrhenius equation lnk = lnA− RT A: Arrhenius constant [35,36]
Ea (kJ mol−1): activation energy
R: universal gas constant (8.314 J mol− 1 K− 1)
  T(K): temperature
ΔS
Eyring equation ln Tk = ln khB + R − ΔH
RT k: rate constant [35,37]
kB: Boltzman constant (1.3807 × 10− 23 J K− 1)
h: Plank constant (6.6261 × 10− 34 Js)
162 S. Chowdhury et al. / Desalination 265 (2011) 159–168

solution pH. At low pH values, the protonation of the functional 100

groups present on the adsorbent surface easily takes place, and
thereby restrict the approach of positively charged dye cations to the
95
surface of the adsorbent resulting in low adsorption of dye in acidic
solution. With decrease in acidity of the solution, the functional
groups on the adsorbent surface become de-protonated resulting in 90

% Adsorption
an increase in the negative charge density on the adsorbent surface

85

80

75

70
0 2 4 6 8 10
pH

Fig. 3. Effect of pH on adsorption of MG using treated rice husk (conditions: weight of

adsorbent = 1.0 g L −1 , agitation speed = 200 rpm, contact time = 180 min,
temperature = 298 K).

and facilitate the binding of dye cations. The increase in dye removal
capacity at higher pH may also be attributed to the reduction of H+
ions which compete with dye cations at lower pH for appropriate sites
on the adsorbent surface. However with increasing pH, this
competition weakens and dye cations replace H+ ions bound to the
adsorbent surface resulting in increased dye uptake.

3.3. Effect of contact time and initial concentration

It is essential to evaluate the effect of contact time required to

reach equilibrium for designing batch adsorption experiments.
Therefore the effect of contact time on adsorption of MG was
investigated. Fig. 4a shows the adsorption of MG by treated rice
husk as a function of contact time at different initial concentrations. It
is seen that the adsorption of MG increased with rise in contact time
up to 20 min. Further increase in contact time did not enhance the
adsorption. Initially, the rate of adsorption was rapid due to the
adsorption of dye molecules onto the exterior surface. After that the
molecules enter into pores (interior surface), a relatively slow process.
The initial faster rates of adsorption may also be attributed to the
presence of large number of binding sites for adsorption and the
slower adsorption rates at the end is due to the saturation of the
binding sites and attainment of equilibrium. Similar conclusions have
been proposed by Khattri and Singh [42] for adsorption of MG by
neem sawdust. The adsorption reached equilibrium within 60 min
and was independent of the initial dye concentration.
The rate of adsorption is a function of the initial concentration of
the adsorbate, which makes it an important factor to be considered for
effective adsorption. Fig. 4b depicts the effect of initial dye
concentration on the adsorption of MG using treated rice husk. It
was observed that as the initial dye concentration increased from
10 mg L−1 to 100 mg L− 1, the adsorption capacity of the treated rice
husk increased (not shown in Fig. 4b). As a rule, increasing the initial
dye concentration results in an increase in the adsorption capacity
because it provides a driving force to overcome all mass transfer
resistances of dyes between the aqueous and solid phase. However as
shown in Fig. 4b, the sorption percentage decreased from 97.16% to
about 89.13%. It can be explained that the adsorbent has a limited
number of active sites, which becomes saturated at a certain
concentration. This indicates that the adsorption capacity will
Fig. 2. Scanning electron micrograph of (a) untreated rice husk, (b) treated rice husk, increase with the increase of initial dye concentration mainly due to
(c) treated rice husk after adsorption of MG. the rise in the mass transfer from the concentration gradient.
 S. Chowdhury et al. / Desalination 265 (2011) 159–168 163

a 3

10 2.5

2
8 10 mg/L

qe, mg/g
20 mg/L
50 mg/L 1.5
100 mg/L 298 K
qe, mg/g

6
1 303 K
308 K
313 K
4 0.5

0
0 20 40 60 80 100
2
t, min

Fig. 5. Effect of temperature on the adsorption of MG using treated rice husk

(conditions: weight of adsorbent = 1.0 g L− 1, agitation speed = 200 rpm, contact
0
time = 120 min, pH 7).
0 20 40 60 80 100 120 140
t, min
rise in temperature may be attributed to increase in the number of
active surface sites available for adsorption, increase in the porosity
b and in the pore volume of the adsorbent. An increase of temperature
increases the rate of diffusion of the adsorbate molecules across the
99
external boundary layer and within the internal pores of the
adsorbent particle, due to decrease in the viscosity of the solution.
97 The enhancement in adsorption may also be a result of an increase in
the mobility of the dye molecules with an increase in their kinetic
energy. The finding is in agreement with the observations of
95
Daneshvar et al [45] on the biosorption of MG on Cosmarium species.
% Removal

The increase of the equilibrium uptake with increase in temperature

93 means that the dye adsorption process is controlled by an endother-
mic process. This phenomenon is characteristic of a chemical reaction
or bonding being involved in the adsorption process [37]. So it is
91 suggested that sorption of MG by chemically modified rice husk may
be a chemical sorption.
89
3.5. Adsorption isotherms

87 In the present study four isotherm equations namely, Freundlich,

Langmuir, Temkin and Dubinin–Radushkevich (D–R) (Table 1) were
85
0 20 40 60 80 100 120
Table 2
Initial dye concentration, mg/L Isotherm parameters for adsorption of MG onto chemically modified rice husk.

Fig. 4. (a) Effect of contact time on MG adsorption onto treated rice husk at different Isotherm Parameters T(K)
initial dye concentrations (conditions: weight of adsorbent = 1.0 g L− 1, agitation 298 303 308 313
speed = 200 rpm, temperature = 298 K). (b) Effect of initial dye concentration on
−1
adsorption of MG using treated rice husk (conditions: weight of adsorbent = 1.0 g L− 1, Langmuir qm ( mg g ) 12.16 15.49 17.76 17.98
agitation speed = 200 rpm, contact time = 120 min, temperature = 298 K, pH 7). KL ( L mg− 1) 0.1597 0.4124 0.6410 1.077
r2 0.975 0.979 0.972 0.966
χ2 0.105 0.108 1.470 0.703
However, the concentration will inversely impact on the adsorption Freundlich KF (mg g− 1) 4.088 5.139 6.527 7.395
frequency because of the limited adsorption sites available for the (L mg− 1)1/n
uptake of cationic dye. Similar observations have been reported by 1/ n 0.722 0.636 0.560 0.522
r2 0.998 0.986 0.992 0.993
Baek et al. [43] and Zhang et al. [44]. χ2 0.064 0.299 0.989 0.060
Temkin KT ( L mg− 1) 9.44 11.20 14.21 15.47
3.4. Effect of temperature BT 1.095 2.057 3.649 4.163
r2 0.954 0.963 0.923 0.956
χ2 0.119 0.825 2.987 1.113
Fig. 5 illustrates the variation of solid phase dye concentrations
Dubinin– qm (mg g− 1) 9.22 11.53 13.38 16.62
with time at different temperatures. From the figure it is seen that Radushkevich
temperature remarkably influenced the equilibrium dye uptake. The β (mmol2 J−2) 6.15 ×10-9 5.98× 10-9 5.39 ×10-9 4.92× 10-9
adsorption of dye increased with increase in temperature indicating E( kJ mol− 1) 9.012 9.143 9.625 10.071
that a high temperature favored MG removal by adsorption onto r2 0.863 0.838 0.762 0.803
χ2 0.493 2.216 4.879 1.025
chemically modified rice husk. The enhancement in adsorption with
164 S. Chowdhury et al. / Desalination 265 (2011) 159–168

20 Table 3
Freundlich parameters for adsorption of MG by various low cost adsorbents.
18
Adsorbent Temp (K) KF 1/n Ref.
16
Hen feathers 303 1.000 0.096 [47]
313 1.000 0.099
14
323 1.000 0.104
Sand — 0.694 0.956 [48]
12
qe, mg/g

Commercially available 303 127.73 0.194 [9]

powdered activated carbon
10
Groundnut shell based 303 143.45 0.128
8 powdered activated carbon
Treated ginger waste 303 1.14 1.075 [38]
Experimental
6 313 1.11 1.030
Freundlich 323 1.04 0.993
Langmuir Bagasse fly ash 303 25.149 0.423 [49]
4
Temkin Activated carbon 303 1.189 0.411
2 D-R (commercial grade)
Activated carbon 303 5.629 0.449
0 (laboratory grade)
0 10 20 30 40 50 60 70 80 90 100 110 Caulerpa racemosa 298 13.10 2.631 [50]
var. cylindracea 308 8.43 1.923
Ce mg/L 318 12.03 1.851
Cellulose powder 298 0.74 0.25 [51]
Fig. 6. Comparison between the measured and modelled isotherms profiles for the Jute fiber carbon 303 32.290 0.285 [52]
adsorption of MG by treated rice husk (weight of adsorbent = 1.0 g L− 1, agitation De-oiled soya 303 2.357 × 10−4 34.482 [40]
speed = 200 rpm, contact time = 120 min, pH 7, temperature: 298 K). 313 2.666 × 10− 4 32.258
323 2.960 × 10− 4 30.303
Bentonite clay 298 1.72 × 10−3 0.724 [53]
fitted to the experimental equilibrium data for MG at different 308 9.91 × 10− 4 0.657
−4
318 8.10 × 10 0.625
temperatures. The results are shown in Table 2 and the modelled −4
328 4.36 × 10 0.512
isotherms are plotted in Fig. 6. The Langmuir isotherm constants KL Degreased coffee bean 298 2.03 1.956 [43]
and qm were calculated from the slope and intercept of the plot 308 0.079 3.484
between Ce / qe and Ce. The values of KL increased with increase in 318 0.007 4.761
temperature, which accounts for the endothermic nature of the Epicarp of Ricinus communis 300 ± 2 2.3046 0.2613 [54]
Maize cob powder 300 11.040 1.0434 [39]
adsorption process.
Rice bran — 8.2553 0.595 [55]
The equilibrium data were further analyzed using the Freundlich Wheat bran 2.3664 0.637
model. The Freundlich constants KF and 1/ n were calculated from the NaOH treated rice husk 298 4.088 0.722 Present study
intercept and slope of the straight line of the plot log qe versus log Ce. 303 5.139 0.636
308 6.527 0.560
The magnitude of 1/n gives a measure of favorability of adsorption.
313 7.395 0.522
The values of 1/n less than 1 represent a favorable sorption. For the
present study the value of 1/n also presented the same trend
representing a beneficial sorption. The increase of Freundlich
constants with increase of temperature confirmed that adsorption E were higher than 8 kJ/mol for all studied temperatures indicating that
was favorable at high temperatures and the process was endothermic the adsorption mechanism was chemical ion-exchange.
in nature. The correlation coefficient (r2) and chi-square (χ2) values of the
The Temkin equation was also fitted to the experimental data. The four isotherms are also listed in Table 2. Based on the error function
constants KT and BT were determined from the intercept and slope of values, the applicability of the isotherms was compared. It could be
the plot between qe andln Ce. Smaller values of the Temkin constant BT concluded that the adsorption of MG onto chemically modified rice
for alkali treated rice husk suggest that adsorption of MG on this husk, best fitted to the Freundlich isotherm equation under the
adsorbent was favorable. As seen from Table 2, BT increased with temperature range studied. The fitness of the adsorption data to the
increasing temperature, indicating endothermic adsorption. Freundlich isotherm implies that that adsorption of MG onto treated
The Dubinin–Radushkevich (D–R) model, which does not assume rice husk was multilayer adsorption applicable to heterogeneous
a homogeneous surface or a constant biosorption potential as the surfaces. A list showing the Freundlich parameters of different low
Langmuir model, was further used to test the experimental data. The cost adsorbents for the sorption of MG from its aqueous solutions is
plots between ln qe and ε2 gave straight lines at all temperatures; given in Table 3. A direct comparison is difficult due to the varying
the values of constants qm and β thus obtained are given in Table 2. experimental conditions employed in those studies. However, from
The constant β gives an idea about the mean sorption energy, E, Table 3, it can be concluded that chemically modified rice husk is an
which is defined as the free energy transfer of 1 mol of solute from excellent adsorbent for MG.
infinity of the surface of the sorbent and can be calculated using
the relationship [35,46]: 3.6. Adsorption kinetics

1 In order to investigate the mechanism of adsorption and its

E = pffiffiffiffiffiffi ð2Þ potential rate-controlling steps that include mass transport and
2β
chemical reaction processes, kinetic models are exploited to test the
experimental data. In this study, the experimental equilibrium data of
The parameter gives information about the type of adsorption MG onto chemically modified rice husk was first analyzed by the
mechanism as chemical ion-exchange or physical adsorption. If the pseudo-first-order and pseudo-second-order kinetic models
magnitude of E is between 8 and 16 kJ mol−1, the sorption process is (Table 1). Table 4 present the results of fitting experimental data
supposed to proceed via chemisorption, while for values of E b 8 kJ mol−1, with pseudo-first-order and pseudo-second-order models using
the sorption process is of physical nature [35,46]. The magnitude of correlation coefficient (R2), coefficient of determination (r2), and
 S. Chowdhury et al. / Desalination 265 (2011) 159–168 165

Table 4 Table 5
Comparison of regression coefficient (R2), coefficients of determination (r2) and chi- Kinetic parameters for adsorption of MG onto chemically modified rice husk.
square test (χ2) for pseudo-first order and pseudo-second-order kinetic models.
Kinetic model Parameters T(K)
Ci ( mg g− 1) Pseudo-first-order Pseudo-second-order
298 303 308 313
R2 r2 χ2 R2 r2 χ2 −1
Pseudo-second- qe, exp (mg g ) 21.32 22.16 23.50 24.92
5 0.854 0.821 3.739 0.996 0.996 0.0320 order qe, cal (mg g− 1) 21.55 22.25 23.71 25.07
−1 -1
10 0.897 0.878 2.377 0.998 0.996 0.0229 k2 (g mg min ) 0.0329 0.0466 0.0804 0.1187
20 0.889 0.864 2.598 0.999 0.998 0.0237 h (mg g− 1 min− 1) 15.27 23.06 45.19 74.60
2
50 0.954 0.934 1.765 1.000 0.999 0.0115 R 0.999 1.000 1.000 1.000
100 0.910 0.899 2.279 1.000 0.999. 0.0111 Elovich α(mg g− 1 min− 1) 1.234 1.951 2.824 3.164
β (mg g-1) 3.092 4.216 5.768 5.495
R2 0.9891 0.9969 0.9915 0.9803
Intraparticle Intercept 1.668 2.892 3.208 3.825
−1 -0.5
diffusion ki(mg g min ) 0.0138 0.0215 0.0283 0.0344
2
also the chi-square test (χ2). From Table 4, a comparison of the error R 0.9210 0.9625 0.9468 0.9431
Liquid film diffusion Intercept -1.54 -1.80 -2.02 -2.34
functions indicate that the pseudo-first-order equation cannot
kfd(min-1) -0.0107 -0.0135 -0.0169 -0.0182
provide an accurate fit of the experimental data. The results suggest R2 0.9815 0.9233 0.9366 0.9733
that pseudo-second-order kinetic model, in contrast to the pseudo-
first-order model, provided a good correlation for the adsorption of
MG on treated rice husk. The plots of t / qt versus t gives straight line the R2 values are close to 1 (Table 4), confirming the applicability of
relation for all the initial dye concentrations studied (Fig. 7a), and all the pseudo-second-order equation. On the other hand, the plots of t /
qt versus t at different temperatures (figure not shown) showed good
a linearity; implying that the adsorption system studied follows the
pseudo-second-order kinetic model. The qe and k2 values were
calculated from slope and intercept of this plots, respectively and
are listed in Table 5. It is observed from Table 5 that rate constant, k2
increases as the temperature increases indicating that adsorption of
MG on treated rice husk was an endothermic process. In addition,
there is only a small difference between the qe, exp and qe, cal,
reinforcing the applicability of the pseudo-second-order model.
From, the pseudo-second-order kinetic parameters, the initial
adsorption rate, h(mg g−1 min− 1) at different temperatures was
calculated using Eq. (3) [56] and are given in Table 5.

2
h = k2 qe ð3Þ

It can be seen in Table 4 that, the value of h increases with increase

in temperature indicating higher temperature favors the adsorption
process by increasing adsorption rate and capacity. The pseudo-
second-order kinetic model provides an accurate description of
sorption kinetics of MG onto treated rice husk for the studied cases
and conditions, and thus supports the assumption behind the model
that the adsorption is due to chemisorption. Similar results were
b previously reported for adsorption of MG onto esterified soybean hull
[57], activated carbon developed from R. communis [54], cyclodextrin-
based adsorbent [10] and chlorella-based biomass [58].
Further the kinetic data was fitted to the Elovich equation
(Table 1). The Elovich equation assumes that the solid surface active
sites are heterogeneous in nature and therefore, exhibit different
activation energies for chemisorptions [59]. The Elovich plot (qt vs.
ln t) at different temperatures is shown in Fig. 7b. The values of the
coefficients α and β are listed in Table 5. The correlation coefficients
(R2) determined from these plots reveal a linear characteristic
(R2 = 0.9969–0.9803). In Elovich model, α is related to rate of
chemisorption (initial adsorption rate) and β is related to surface
coverage (desorption constant). With the increase in temperature, the
constants α and β increased showing that both the rate of
chemisorption and the available adsorption surface would increase.
In many adsorption processes, the adsorbate species are most
probably transported from the bulk of the solution into the solid phase
through intraparticle diffusion/transport. So the intraparticle diffusion
is another kinetic model which should be used to study the rate of MG
adsorption onto treated rice husk. The possibility of intraparticle
diffusion was explored by plotting qt versus t0.5. The plots of qt versus
Fig. 7. (a) Pseudo-second-order kinetics for adsorption of MG at different initial
t0.5 were linear (figure not shown) and the R2 values were between
concentration using treated rice husk. (b) Elovich kinetic plots for adsorption of MG 0.9210 and 0.9625. It can be generally stated that adsorption process
onto treated rice husk at different temperatures. tends to follow intraparticle diffusion. However, if the intraparticle
166 S. Chowdhury et al. / Desalination 265 (2011) 159–168

diffusion is the sole rate-limiting step, it is essential for the qt versus Table 6
t0.5 plots to pass through the origin. As the plots did not have a zero Thermodynamic parameters and isosteric heat of adsorption of MG onto chemically
modified rice husk.
intercept, it may be concluded that surface adsorption and intrapar-
ticle diffusion were concurrently operating during interaction of MG Thermodynamic parameters
with treated rice husk. Sl. No Temperature (K) ΔG0 (kJ mol− 1) ΔH0( kJ mol− 1) ΔS0( J mol− 1 K−1)
The diffusion of the adsorbate from the bulk liquid phase to the
1 298 −6.18 63.76 234.4
surface of the adsorbent might also play an important role in 2 303 −7.09
determining the rate of an adsorption process. Therefore the kinetic 3 308 −8.40
data were analyzed by the liquid film diffusion model (Table 1). The 4 313 −9.65
plots of ln(1 − F)versus t with zero intercept would suggest that the
kinetics of the adsorption process is controlled by diffusion through Isosteric heat of adsorption
the liquid film surrounding the solid adsorbents. The plots of ln(1 − F) Sl. No qe ( mg g− 1) ΔHX( kJ mol− 1) R2
versus t (figure not shown) were found to be linear (R2 = 0.9233– 1 2 78.630 0.9614
0.9815) with intercepts in the range of –1.54 to –2.34. The rate 2 4 79.699 0.9685
constant, kfd, had values ranging from –0.0107 to –0.0182 min-1 3 6 81.264 0.9555
(Table 5). The linear plots did not pass through the origin suggesting 4 8 83.848 0.9638
5 10 89.132 0.9465
limited applicability of the liquid film diffusion model in the present
adsorption system.

3.7. Activation parameters

adsorption onto treated rice husk. The increase of the absolute value of
ΔG0 as temperature rises indicates that the affinity of MG on alkali
From the pseudo-second-order rate constant k2 (Table 5), the
treated rice husk was higher at high temperature. The positive value of
activation energy Ea for adsorption of MG onto treated rice husk was
ΔH0 (63.76 kJ mol− 1) confirms that the adsorption reaction is
determined using the Arrhenius equation (Table 1). By plotting ln k2
endothermic. The positive value of ΔS0 (234.4 J mol− 1 K− 1) reflects
versus 1/ T (figure not shown), Ea was obtained from the slope of the
the affinity of the treated rice husk for MG and an increased
linear plot. The value of Ea was 68.12 kJ mol− 1. The magnitude of Ea
randomness at the solid-solution interface during adsorption [60].
may give an idea about the type of adsorption. According to literature
[36], the process may be an activated chemical adsorption process.
The Eyring equation was used to calculate the standard enthalpy 3.9. Isosteric heat of adsorption
(ΔH#), and entropy of activation (ΔS#) were calculated using the
Eyring equation (Table 1). The values of ΔH# and ΔS# were calculated Isosteric heat of adsorption (ΔHX, kJ mol−1) defined as the heat of
from the slope and intercept of the plot of ln(k2 / T) versus 1/ T (figure adsorption determined at constant amount of adsorbate adsorbed is
not shown). The free energy of activation (ΔG#) was obtained from: one of the basic requirements for the characterization and optimiza-
ΔG# = ΔH# − TΔS#. The values of ΔG# were found to be (75.76, 77.93, tion of an adsorption process. Knowledge of the heats of sorption is
78.10, 80.27) kJ mol− 1 at T = (298, 303, 308 and 313) K respectively. very important for equipment and process design. The isosteric heat
The large positive values of ΔG# suggests that energy was required in of adsorption at constant surface coverage (qe = 2, 4, 6, 8, 10 mg g− 1)
the adsorption reaction to convert reactants into products. The was calculated using the Clausius–Clapeyron equation [36,61]:
positive value of ΔH# (65.53 kJ mol− 1) indicates endothermic
process. The negative value of ΔS# (−124.34 J mol−1 K−1) suggests
that MG adsorption onto chemically modified rice is an associative dðln CeÞ ΔH
= − 2X ð7Þ
mechanism [37]. dT RT

3.8. Thermodynamic parameters

For this purpose, the equilibrium concentration (Ce) at constant
The thermodynamic parameters such as Gibbs free energy change amount of dye adsorbed was obtained from the isotherm data at
(ΔG0), enthalpy (ΔH0) and entropy (ΔS0) were calculated using the different temperatures. The values of ΔHX were obtained from the
following equations [36]: slope of a plot of ln Ce versus 1/ T for different amounts of adsorbate
onto adsorbent. The plots of lnCe versus t were found to be linear
0
ΔG = −RT ln KC ð4Þ (Fig. 8a). The values of ΔHX were determined from the slope of the
plots. The R2 values of the isosteres and the corresponding ΔHX values
0
ΔG = ΔH −TΔS
0 0
ð5Þ are listed in Table 6. For physical adsorption ΔHX should be below
80 kJ mol−1 and for chemical adsorption it ranges between 80 and
where KC is the distribution coefficient for adsorption and is 400 kJ mol− 1 [62]. In the present system, the values of ΔHX were
determined as: between 78.63 and 89.13 kJ mol− 1 indicating that the adsorption of
MG onto treated rice husk was a chemical process involving ion
Ca exchange. The variation of ΔHX with surface loading is presented in
KC = ð6Þ
Ce Fig. 8b. It is observed that the ΔHX values increased steadily with an
increase in qe indicating that chemically modified rice husk was
where Ca is the equilibrium dye concentration on the adsorbent (mg L− 1) having heterogeneous surfaces. The dependence of ΔHX on surface
and Ce is the equilibrium dye concentration in solution (mg L− 1). coverage can be due to adsorbate-adsorbate interaction followed by
The Gibb's free energy (ΔG0) for adsorption of MG onto treated rice adsorbate-adsorbent interaction. Initially, at lower qe values, adsor-
husk obtained at all temperatures are listed in Table 6. ΔH0 and ΔS0 bate-adsorbate interaction takes place resulting in low ΔHX values. As
were determined from the slope and intercept of the plot of ΔG0 versus qe increases, adsorbate-adsorbent interaction occurs resulting in high
T (figure not shown) and are also tabulated in Table 6. The values of heats of adsorption. Variation in ΔHX with surface loading can also be
ΔG0 were negative at all temperatures and the negative values confirm attributed to the possibility of having lateral interactions between the
the feasibility of the process and the spontaneous nature of MG adsorbed dye molecules.
 S. Chowdhury et al. / Desalination 265 (2011) 159–168 167

a In this study, the removal of MG by adsorption on chemically

modified rice husk was found to be rapid at the initial period of
contact time and then to become slow and stagnate with the increase
in contact time (Fig. 4a). The adsorption was strongly pH-dependent
(Fig. 3). MG was adequately adsorbed for pH between 4.0 and 9.0. It
was also observed that the modeling of intraparticle diffusion showed
a contribution of film diffusion on the control of sorption kinetics;
however intraparticle diffusion was not the dominating mechanism.
The pseudo-second-order kinetic model provides best correlation
with the experimental data for the adsorption of MG onto chemically
modified rice husk.
According to the experimental findings of the present study, and
based on the structure of the adsorbate and adsorbent surface
properties, the mechanism for the removal of MG by adsorption on
treated rice husk may be assumed to involve the following steps:

• Migration of dye from bulk of the solution to the surface of the

adsorbent
• Diffusion of dye through the boundary layer to the surface of the
adsorbent
• Adsorption of dye on the surface of treated rice husk, which may be
b due to the formation of surface hydrogen bonds between the
hydroxyl groups on the rice husk surface and the nitrogen atoms of
MG as suggested in Fig. 9 or through a possible mechanism of a dye–
hydrogen ion exchange process as shown below:
 þ
Rice Husk—OH⇌Rice Husk—O þ H

 þ þ
Rice Husk—O þ MG ⇌Rice Husk—O—MG þ H

• Intraparticle diffusion of dye into the interior pores of the adsorbent

In order to confirm this mechanism, more experiments need to be

carried out using other cationic dyes.

3.11. Cost analysis

Adsorbent cost is an important parameter for comparing the

industrial application of adsorbent materials; however it is seldom
reported in the literature [3]. The overall cost of the adsorbent
Fig. 8. (a) Plots of ln Ce against 1/T for adsorption of MG onto treated rice husk. (b) Plot
of isosteric heat of adsorption against surface loading for adsorption of MG onto treated
rice husk.

3.10. Adsorption mechanism

The major challenge in an adsorption study is to elucidate the

adsorption mechanism. However, before understanding the adsorp-
tion mechanism it is necessary to consider to two points: firstly the
structure of the adsorbate; and secondly the adsorbent surface
properties. In this connection, it must be pointed out that MG is a
cationic dye having two amino groups. On the other hand, rice husk
consists of cellulose, hemicelluloses, lignin and silica as its main
components, besides other minor constituents such as crude protein,
fats, waxes etc [19,20]. Both cellulose and hemicellulose contain
majority of oxygen functional groups which are present in lignocel-
lulosic materials such as hydroxyl, ether, and carbonyl, while lignin is
a complex, systematically polymerized, highly aromatic substance,
and acts as a cementing matrix that holds between and within both
cellulose and hemicelluloses units. Silica is present on the outer
surface of rice husk in the form of silicon-cellulose membrane and acts
as a natural protective layer [21]. Chemical modification of rice husk
with sodium hydroxide removes silica, lignin and other impurities
from the rice husk surface thus revealing chemically reactive Fig. 9. Schematic representation of hydrogen bonding between nitrogen atoms of MG
functional groups like –OH. and hydroxyl groups on the treated rice husk surface, cellulose unit.
168 S. Chowdhury et al. / Desalination 265 (2011) 159–168

Table 7 that chemically modified rice husk can be an alternative economic

Total cost for preparing 1 kg of the adsorbent. material to more costly adsorbents used for dye removal in
Sl. no Material Unit cost, INR Amount used Net price, INR wastewater treatment processes.
1 Sodium hydroxide 188.00 kg−1 50 g 9.40
2 Cost of autoclaving 2.50 kWh− 1 0.75 kWh 1.87 Appendix A. Supplementary data
(10 psi: 15 min)
3 Cost of drying 2.50 kWh−1 7.20 kWh 18.00 Supplementary data to this article can be found online at
(343 K: 9 h)
doi:10.1016/j.desal.2010.07.047.
4 Net cost 29.27
5 Other overhead costs 2.92
(10% of net cost) References
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