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Materials Chemistry and Physics 108 (2008) 263–268

Kinetic model for the isothermal activation of bentonite by sulfuric acid

H. Babaki, A. Salem ∗ , A. Jafarizad
Chemical Engineering Department of Sahand University of Technology, Tabriz, Iran
Received 11 March 2007; received in revised form 24 September 2007; accepted 27 September 2007

Abstract
The activation mechanism of typical bentonite powder with sulfuric acid was studied from variations in their surface area during the reaction. The
surface area of activated samples at different activation temperatures and times were measured by methylene blue adsorption to quantify the effect
of acid. The influence of activation time was investigated by isothermal experiments, performed at different temperatures. The specific surface
area–time data were analyzed by using a modified kinetic model and the values of kinetic parameters were calculated. Also, the influence of acid
concentrations on kinetic parameters was evaluated. The validity of proposed model to describe the bentonite activation kinetic was substantiated
by computation of reaction time to achieve maximum value of specific surface area in other temperatures.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Bentonite; Activation; Specific surface area; Kinetic model

1. Introduction There are three types of pores in bentonites as in most solids.

Empty spaces in a solid that are smaller than 2 nm are called
Bentonite is the best known member of clay group that con- micropores, those between 2 and 50 nm are called mesopores
tains montmorillonite crystal. The montmorillonite structure is and those larger than 50 nm are called macropores. Although the
classified as dioctahedral, having two thirds of octahedral sites micropores and mesopores lie within the particles, the macro-
occupied by trivalent cations. Dioctahedral montmorillonite has pores lie between the particles. The adsorption capacity of
its structural charge originating from the substitution of Mg2+ the macrospores is at negligible level compared to that of the
for Al3+ in octahedral sheet. The idealized structural formula microspores and mesopores. Bentonites are the most important
for montmorillonite is M+ y ·nH2 O (Al2y Mgy ) Si4 O10 that M is a among solids that contain natural mesopores. They also, contain
cation. The negative charge is balanced by cations intercalated a small amount of micropores. The large amount of smectite
between structural units and these cations may be alkali earth minerals contained in bentonites is the main sources of porosity.
ions such as Na+ or the alkaline metals: Ca2+ and Mg2+ [1]. The physico-chemical properties of bentonites such as absorp-
When Ca2+ cations are exclusively exchange with montmoril- tion and catalytic activity depend extensively on the micro- and
lonite surface, the clay is known as Ca-montmorillonite. Illite meso-pores [3].
also, is the second important mineral can be found in bentonite Activation is the chemical or physical treatment applied to
composition having K+ ions [1]. certain types of clays to develop a capacity to absorb coloring
The application range of bentonites, depend on the kinds and matter and other impurities in oils and solutions [4]. The term
amount of its montmorillonite, other clay minerals and non- of activity denotes chemical and physico-chemical reactivity,
clay crystals [2]. The application of bentonites in production of whose increase is usually traceable to an increase in surface
selective adsorbents, bleaching earth, catalyst beds, carbonless area of solid [5].
copy paper and medication depends on the pores structure of Activation of bentonite by acid is an important step for
montmorillonite. adsorption of some impurities by active clay [6]. This is so-called
“activation process”. The activation of bentonite is carried out
in a continuous stirred tank reactor at low temperatures between
70 and 120 ◦ C in the presence of activation agents, mostly sul-
∗ Corresponding author. Tel.: +98 4123459159; fax: +98 4123444355. furic acid [7]. During the reaction, the surface area of bentonite
E-mail address: [email protected] (A. Salem). increases due to decomposition of smectite structure [6].

0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.09.034
264 H. Babaki et al. / Materials Chemistry and Physics 108 (2008) 263–268

The most significant mechanism in the activation of natural

bentonite is cation exchange by H+ ions. During the activation
process, a considerable amount of cations were substituted by
hydrogen cations which increases the specific surface area [8].
These transformations in montmorillonite and illite layers give
rise to significant changes in cation exchange capacity (CEC),
chemical and mineralogical characteristics of bentonite [7].
The theoretical models put forward by different investiga-
tors to describe the activation process in presence of acid,
performed by methylene blue adsorption. In developing the
model, the adsorption of methylene blue on surface of acti-
vated bentonite was assumed to be due to increasing electrical
charge of particles, during there reaction with acid [9]. These
assumptions, required in mathematically developing models,
were based on simplifications of the true microstructure of clay
Fig. 1. Specific surface area–time plots for activation of bentonite by 3 mol L−1
[10]. The Langmuir theoretical exaggerated equation use to
sulfuric acid.
describe the adsorption of methylene blue on surface area of
bentonite [10,11]. This model therefore only has an approxi- of clay depends on the relative concentration of negatively charged sites on the
mation of methylene blue adsorption, determining the relative clay particle surfaces and the surface area of the clay per unit mass [16,17].
influence of some kinetic factors such as pH and time [12,13]. Methylene blue powder (Merck C.l. 52015) was used in this study. The
In activation process based on natural clays the surface methylene blue solution was prepared by mixing 1.0 g of dry powder with
area changes continuously owing to cation exchange in struc- 200 mL of deionized water. The clay suspension also, was obtained by mix-
ing 10 g of oven-dry clay with 30 mL of deionized water and the methylene blue
ture of clay [14,15]. Since the variations in cation positions solution was added to the clay suspension in 0.5 mL increments. After the mix-
are very complex, the use of theoretical model proposed in ing of suspension (1 min for the each addition of methylene blue) a small drop
the literature are not applicable to estimate the surface area of it was removed and placed in Fisher brand filter paper P5. Methylene blue
[12]. In this work a new kinetic model has been proposed to coats all the mineral surfaces and the end point is obtained when the unabsorbed
describe isothermal activation of natural bentonite. First, the methylene blue forms a permanent light blue halo around the clay aggregate spot.
The relationship between specific surface area and required methylene blue to
kinetic parameters of model were calculated by experimental reach the end point is:
data and the effect of sulfuric acid concentration on these param-
1 1
eters was evaluated thereafter, the validity of model was shown S= (0.5N)AV AMB (1)
319.87 200
to estimate maximum specific surface area at each tempera-
ture. where N is the number of methylene blue increments added to the clay suspension
to form halo around clay, Av the Avogadro’s number (6.02 × 1023 mol), and
AMB is the area covered by one methylene blue molecule (typically assumed to
2. Materials and methods be 130 Å2 ). The entire experimental procedure was found to give satisfactory
reproducible results [17].
The experiments were carried out in small-scale batch experiments setup. For
this purpose natural bentonite was applied. For the study of activation process 3. Results and discussion
sulfuric acid, 98 wt%, was used. The chemical analysis of bentonite, presented
in mass percent, was determined as follows: Na2 O, 0.28; K2 O, 0.27; CaO, 1.48;
MgO, 2.13; Al2 O3 , 12.17; TiO2 , 0.10; Fe2 O3 , 0.57; SiO2 , 72.75; SO3 , 0.80;
Specific surface area–time plots shown in Figs. 1–3 refer
and L.O.I, 9.34. The main minerals identified by XRD method in bentonite are: activation of bentonite by sulfuric acid for there activated con-
montmorillonite, illite and opal-CT.
In all of the present study fine-sized bentonite (−200 mesh), comparable
with that used in industrial practice was selected. Dry bentonite powders and
sulfuric acid with concentrations of 3, 4 and 5 mol L−1 were separately prepared
and mixed thoroughly in to three-neck flask. The experimental setup consisted
of a 1000 mL flask equipped a condenser. A weighed quantity of charge (10 g of
bentonite and 100 mL of acid solution) was mixed thoroughly into the flask. The
samples prepared as above, were activated at 30, 50, 70, 90 ◦ C and during 15,
30, 45, 60, 90 and 120 min. The flask containing suspension was heated using
laboratory heater and temperature was controlled by thermometer. The zero time
was counted when the suspension temperature reached to desired temperature.
The surface area was measured by methylene blue as following procedure [16].
Methylene blue dye has been used to determine the surface area of clay
minerals for several decades. The chemical formula is C16 H18 ClN3 S with a
corresponding molecular weight of 319.86 g mol−1 . Methylene blue in aqueous
solution is a cationic dye, C16 H18 N3 S+ , which is a large polar organic cation and
is absorbed onto the negatively charged surfaces of clay minerals. Hence, the
specific surface of particles can be determined by amount of absorbed methylene
blue. The surface area covered by one methylene blue molecule is typically Fig. 2. Specific surface area–time plots for activation of bentonite by 4 mol L−1
assumed to be 130 Å2 . The amount of methylene blue absorbed by given mass sulfuric acid.
 H. Babaki et al. / Materials Chemistry and Physics 108 (2008) 263–268 265

centration tested. All the curves are identical in nature and are
characterized by exponential behavior. This kind of behavior
is generally observed in reaction involving cation exchange
in the solids structures [7]. In the present investigation, the
observed exponential behavior can be attributed to cation dis-
solving involved in total surface area. The obtained results show
that the specific surface area increases with reaction time as
sample activates, except for temperature and times that sample
undergoes fast decomposition followed by breakdown reaction
in layer of montmorillonite and illite. First, the rise in specific
surface area is a result of unoccupied octahedron and tetrahedron
spaces remaining from Mg2+ , Fe3+ and Al3+ ions that have left
the layers of montmorillonite and illite crystals. As the activa-
tion progresses, the empty spaces grow larger and micropores are
transformed into mesopores. Finally, because of the decomposi-
tion of crystal structure at some locations, some of the mesopores
disappear, leading to a drop in specific surface area [7]. It is obvi- Fig. 4. Application of modified kinetic model to activation of bentonite by
3 mol L−1 sulfuric acid.
ous that the rate of activation increases as acid concentration
rises.
determines the specific surface area characteristics. Thus for
To obtain the kinetic parameters and thereby to calculate the
b = 1 the specific surface area change follows homogeneous first-
maximum specific surface area of each condition a modified
order kinetic. For b < 1 an exponential behavior is guaranteed.
kinetic model has been proposed to specific surface area–time
The model given by Eq. (2) is a general one and is applicable to
data from Figs. 1–3. This significantly simple mathematical
all temperatures. The linear equation for modified kinetic model
model depicts structural changes taking place in the matrix of
can be written as:
bentonite during the activation process and also accounts for  
exponential behavior of specific surface area–time variations. S
ln ln = ln a + b ln t (3)
Since the activation of bentonite by sulfuric acid occurs by cation S0
exchange and goes through a substitution of metallic cation by
A linear plot of ln ln(S/S0 ) versus ln t will give slope b and
H+ , application of this model is justified. The proposed model
intercept a. Figs. 4–6 show the fitting of kinetic model for acti-
is:
vation of bentonite by sulfuric acid at different concentration
S = S0 exp(at b ) (2) of sulfuric acid. It is interesting to see that specific surface
area–time data of bentonite activated by sulfuric acid fit the
where S0 and S are the initial and activated specific surface area modified kinetic model very nicely in all temperatures. From
of bentonite respectively, t the activation time in minute, a and the slopes and intercepts of linear plots model parameters, b and
b are the constant parameters. Model parameter, a, is related to a, were calculated. By use of the parameter values (a and b)
the kinetic rate constant of reaction and is temperature depen- the rate constant was obtained for each temperature. The val-
dent. Parameter b is related to physical changes occurring in the ues of a and b have been tabulated in Table 1. It is observed
bentonite matrix. Parameter b is very important since its value that the value of b virtually remains constant whilst the param-

Fig. 3. Specific surface area–time plots for activation of bentonite by 5 mol L−1 Fig. 5. Application of modified kinetic model to activation of bentonite by
sulfuric acid. 4 mol L−1 sulfuric acid.
266 H. Babaki et al. / Materials Chemistry and Physics 108 (2008) 263–268

Fig. 6. Application of modified kinetic model to activation of bentonite by Fig. 7. Variation of rate constant with temperature.
5 mol L−1 sulfuric acid.

Table 1 k(S), corresponding to specific surface area varies continuously

The parameters of modified kinetic model at different concentrations of sulfuric with time due to continues structural change in bentonite matrix.
acid The activation rate constant has been expressed as the average
Acid concentration T (◦ C) a b ra value, k:
(mol L−1 ) S
S k(S)d S
30 0.4365 0.2292 0.997 k= 0 (5)
50 0.5467 0.2231 0.986
S − S0
3
70 0.6334 0.2197 0.991 The expression for the rate constant, k(S), given by following
90 0.7636 0.2147 0.996
equation:
30 0.3915 0.3101 0.995   (b−1)/b
50 0.4655 0.3118 0.991 S
4 k(S) = a1/b b ln (6)
70 0.5291 0.3132 0.991 S0
90 0.5696 0.3211 0.986
30 0.3839 0.3570 0.997 k(S) can be calculated at 10 times ratio of specific surface area
50 0.4342 0.3514 0.991 increment, i.e. by substituting S/S0 = 10 in Eq. (7). Arrhenius
5
70 0.4904 0.3581 0.994 plots for three typical cases were shown in Fig. 7 as following
90 0.5351 0.3581 0.995 equation:
a Linear coefficient.  
Ea
k = k0 exp − (7)
eter a increases considerably when activation temperature rises. RT
The values have been plotted versus the inverse of temperature, where Ea is the activation energy, k0 the frequency factor and R is
on semi-logarithm scale according to Eq. (4). The plots were the constant of ideal gas. The values of kinetic parameters were
observed to fit a straight line well, which indicates that varia- represented in Table 3. It is observed that the value of activation
tion of parameter a with temperature may be represented by an energy decreases as acid concentration rises. This phenomena
Arrhenius-like equation form as: indicates that the mechanism of structural changes in bentonite
  matrix, are different in all acid concentration. It is to be noted that
Q
a = a0 exp − (4) during activation process, specific surface area development in
T
bentonite matrix involves typically with pore development that
where a0 and Q are the constant parameters of Eq. (4) and Table 2 increases as acid concentration reach to 5 mol L−1 . As activation
details the value of these parameters. Since in the activation process progresses the Mg2+ , Fe3+ and Al3+ leave the octahedral
process, the rate of activation defined in terms of rate constant, and tetrahedron layers and the mentioned cation spaces remain

Table 2 Table 3
The parameters of Eq. (4) at different concentrations of sulfuric acid The constants of Arrhenius equation at different concentration of sulfuric acid
Acid concentration a0 Q (kJ mol−1 ) r rms% Acid concentration Ea (kJ mol−1 ) k0 (s−1 ) r
(mol L−1 ) (mol L−1 )

3 9.257 63.02 0.997 3.74 3 30.63 70.93 0.998

4 3.906 47.80 0.992 6.20 4 21.25 11.2 0.998
5 2.933 42.56 0.999 6.27 5 14.99 2.06 0.991
 H. Babaki et al. / Materials Chemistry and Physics 108 (2008) 263–268 267

Fig. 10. Statistical evaluation of specific surface area for activation of bentonite
Fig. 8. Statistical evaluation of specific surface area for activation of bentonite by 5 mol L−1 sulfuric acid.
by 3 mol L−1 sulfuric acid.
The values of specific surface area computed by Eq. (8)
have been plotted versus those determined experimentally in
empty [7]. As the acid concentration increases the empty layer
Figs. 8–10. To compare the experimental data with model pre-
spaces grow and the fraction of micropores increases. In this
diction, the percent deviations, Dv , were calculated between
case probably micropores are merged, increasing the number
experimental data points and theoretical correlation predictions
mesopores, however at the same time new pores are formed but
by following equation:
the trends of these changes in pore size show an overall positive
 
effect on specific surface area. Therefore specific surface area Scal − Sexp
increases considerably and activation energy was drop. The addi- Dv = × 100 (9)
Sexp
tion of acid concentration results a decrease in pre-exponential
factor. Finally, the variations of kinetic parameters show that the From these percent deviations overall percent root mean
rate of activation improves. square, rms%, deviations were then calculated as follow:
The following equation which relates the variation of specific  N
1/2
surface area of studied bentonite to activation time and temper-  D2 v
rms% = (10)
ature was obtained by taking into account Eq. (4) and average N
i=1
value of b:
   Very good agreement can be observed between the experi-
Q
S = S0 a0 exp − t ḃ (8) mental data and calculated values with acceptable percent rms
T deviations reported in Table 2, which substantiates the validity
of modified kinetic model.
In order to well understand the validity of modified kinetic
model we calculated the values of activation time to be able to
reach maximum values of surface area for other temperatures
(30, 50, 70 ◦ C). The maximum value of specific surface area
at 90 ◦ C was obtained 108.6 m2 g−1 as shown in Fig. 3. The
following equation was related the optimum activation time to
temperature:
B
ln topt = A + (11)
T

Table 4
Optimum activation time vs. temperature at different concentration of sulfuric
acid
Acid concentration A B
(mol L−1 )

3 −5.0309 4115.6
4 −0.7965 2202.8
Fig. 9. Statistical evaluation of specific surface area for activation of bentonite 5 0.1089 1726.7
by 4 mol L−1 sulfuric acid.
268 H. Babaki et al. / Materials Chemistry and Physics 108 (2008) 263–268

4. Conclusion

Activation of bentonite by sulfuric acid is a typical example of

cation exchange proceeding through liquid phase. Since smec-
tite decomposition controls specific surface area in activation
process, increasing acid concentration which enhances decom-
position rate, is also enhances the rate of bentonite activation.
The temperature was found to increase smectite decomposi-
tion rate which produces enhanced activation rate and increases
specific surface area of bentonite correspondingly. The valid-
ity of proposed modified kinetic model to describe activation
process of bentonite by sulfuric acid was substantiated. The
model can also be used for clays that are activated by other
solutions.

References
Fig. 11. Optimum activation time vs. temperature at different concentration of
sulfuric acid.
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