XANTHATED COAL AS A LEAD CATION EXCHANGER FOR

ENVIRONMENTAL REMEDIATION

VÁSQUEZ-OSORIO, Yelitza 1, ESPINOSA-FUENTES, Eduardo Antonio 2, COLPAS-

CASTILLO, Fredy 1, MEZA-FUENTES, Edgardo 1 and FERNANDEZ-MAESTRE, Roberto 1*
1 Programa de Quimica, Campus de San Pablo, Universidad de Cartagena, Zaragocilla, Cartagena, Colombia
2 Corporación Universitaria de la Costa (CUC), Barranquilla, Colombia,

*Corresponding autor rfernandezm@unicartagena.edu.co tel 575-6469578 fax 575-6698180

Received 12 June 2000; received in revised form 30 November 2000; accepted 14 December 2000

RESUMO

Palavras-chave:

ABSTRACT
High concentrations of heavy metals in industrial effluents has led to contamination of natural water
bodies. To remove these heavy metals, we prepared a cation exchanger from coal (OC) modified by treatment
with CS2 and NaOH, to obtain xanthated coal (XC). Lead removal was best at pH 5 with adsorption of 74% and
98% for OC and XC. The adsorption reached equilibrium at 120 min (pseudo-second order kinetics). Isotherms
showed OC best suited to Langmuir isotherm but, once xanthated, to Freundlich. Coal xanthation has been rarely
reported and produces new carbon materials through the modification of low rank coal.

Keywords: coal, adsorption, xanthates, lead, cation exchangers

INTRODUCTION Blancas et al. 2013; Chakraborty and Tare 2006).

Xanthates are formed by reacting an organic
Pollution of water bodies with lead and substrate containing hydroxyl groups with carbon
other heavy metals has endangered the health of disulfide under basic conditions (Liang et al. 2009):
humans and animals because, as they do not
− +
degrade in the environment, metals accumulate in 𝐶𝑜𝑎𝑙 − 𝑂𝐻 + 𝐶𝑆2 + 𝑁𝑎𝑂𝐻 → 𝐶𝑜𝑎𝑙 − 𝑂𝐶𝑆2 + 𝑁𝑎
living tissues causing serious diseases and
disorders due to their toxic and carcinogenic The chemical composition of mineral coal
effects (Ngah and Hanafiah 2008). To remove makes it an ideal substrate for the synthesis of
these heavy metals from wastewater various xanthates for its high content of hydroxyl functional
conventional methods have been used; however, groups. Retention of heavy metals from the
these methods are not economical or effective incorporation of xanthate groups in carbonaceous
when the concentration of metals is low (Torres materials has been investigated by several
Blancas et al. 2013). Coal has some ion exchange researchers (Chammui et al. 2014). Haenel (1992)
capacity in its natural structure (Féris et al. 2000) used xanthation to increase the content of
that can be increased by chemical modification of functional groups for complexation of metals in
its surface (Orjuela et al. 2000; Vassileva and coal through the free electrons in carbon disulfide,
Detcheva 2011). These modifications can be CS2.
carried out with sulfur groups, characterized by a The experimental data is validated with
high affinity for heavy metals. Among sulfur different models of adsorption isotherms.
groups, xanthates show a strong binding to heavy Although, such adsorption models were initially
metals and have been used to increase the developed for gas adsorption on solids they can
adsorption capacity of different materials (Torres be applied to chemisorption on a surface. The

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adsorption models of Freundlich and Langmuir are
mainly used in the processes where the The effect of pH on the adsorption of Pb2+
phenomenon of chemisorption occurs which is was examined through a mixture of 50 mg of XC
typical of ion exchange phenomena using and OC with 10 ml of 100 ppm Pb2+ at 25°C.
exchange resins. These isotherms are mainly Analyses were performed at pH values of 3 to 5
used for the study of catalysis phenomena at the adjusted by adding 0.1 mol L-1 HNO3 solution and
industrial level and are those that are mainly used 0.1 mol L-1 NaOH. After 3 h stirring, the solutions
in the literature for the characterization of ion were filtered and the filtrate concentration was
exchange phenomena of metals in exchange determined.
resins (Silgado, Marrugo, and Puello 2014; For the kinetic study of Pb2+, 500 mg of
Šćiban, Klašnja, and Škrbić 2006). adsorbent were mixed with 100 ml of 100 ppm of
We investigated the preparation of an Pb2+ at pH 5 for 2.2 h and 25 ° C. Samples were
adsorbent from the incorporation of xanthate withdrawn at different time intervals to determine
groups on the carbon surface and the evaluation the concentration of lead. Pb2+ adsorption
of its Pb2+ adsorption from aqueous solutions by experiments were carried out mixing 50 mg of the
kinetic studies and pH for optimum adsorption. adsorbent with 10 mL of Pb2+ at 25, 50, 100, 200
or 400 ppm, pH 5, 2 h and 25 °C. The amount of
2. Material and methods adsorbed metal was determined using:

2.1. Instrumental C0 V0 - Ce V0
qe = m
(Eq. 1)
Metal concentrations were determined by
Where C0 is the initial concentration of Pb2+ in mg
flame atomic absorption spectrometry (ICE 3000,
L-1, V0 the initial volume of the solution in L, Ce
Thermo Scientific, Zeeman correction). Other
the Pb2+ concentration at equilibrium in mg L-1
parameters were measuring time: 4.0 s and
and m the adsorbent mass in grams.
number of replicate analyses, 3. Solutions were
prepared with a sodium acetate/acetic acid buffer
2.4. Specific Surface Area
and the ionic strength was adjusted with NaCl.
Infrared spectra of the adsorbents were obtained
To obtain nitrogen adsorption isotherms by
by mixing one mg of coal with 100 mg of KBr,
the BET method, we used a Gemini II 2375
compressing to obtain a pellet that was analyzed
apparatus (Micromeritics, Norcross, GA, U.S.A.).
on an FTIR (SHIMADZU-8400) in the 4000-400
The analysis had the following steps: 0.200 g of
cm-1 range.
sample in a tube, was heated at 200°C, subjected
to vacuum up to a pressure of 2 μm Hg, and
2.2. Coal xanthation
weighted. we later graphed 1/[Vads (po/p-1)] versus
p°/p in the 0.01-0.1 pressure relative range to
A subbituminous coal sample, from La measure specific surface area. The I-point
Loma Cesar mine (Colombia), was swelled for 7
(inflection point) was determined using V(1-p/p°)
days with acetone, washed with distilled water and
versus po/p, or V(1-p/p°)/(p/po) versus V(1-p/p°)
dried at 70 °C for 24 h. Subsequently, it was milled
(Ladavos et al. 2012). The linear range of p versus
in a ball mill, sieved to 0.225 mm, washed with 0.1
p/Vads graph was used to calculate the Langmuir
mol L-1 HCl and distilled water to neutral pH, and area. The textural characterization of the solid
dried at 70°C for 24 h to remove possible
obtained with the adsorption isotherms is
contaminants and colored substances. The
important because it gives us information about
product obtained was named OC. Later, 25 grams
the pore size distribution. This is important in
of coal were taken, 424 mL of a 4 mol L-1 NaOH
determining the type of adsorbate that can diffuse
solution was added using a 0.06 carbon/NaOH into the pores and be chemically exchanged on the
w/w ratio stirring for 3 hours, and later 102 mL of
surface of the adsorbent. For this reason, it is
CS2 with a 4.08 CS2/coal w/w ratio and stirring for
important to determine the selectivity that some
4 hours. The mixture was allowed to stand for 16
materials show towards a certain type of for certain
hours, filtered, washed several times with
types of analytes.
deionized water and dried at 70°C (Chakraborty
and Tare 2006). This product was designated XC.
RESULTS AND DISCUSSION
2.3. Adsorption Experiments

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3.1. Effect of pH
One important property of adsorbents is the speed
The effect of pH on the adsorption of Pb2+ in OC with which the adsorbate is adsorbed and reaches
and XC is shown in Figure 1, which shows that pH equilibrium. The mathematical model that
affected the adsorption of Pb2+ in aqueous describes the amount of Pb2+ adsorbed at a zero
solution. At low pH, there is a poor adsorption of time and at a specific time, is given by:
Pb2+ as a result of the strong electrostatic
repulsion of H+ ions on the carbon surface with the mg Pb2+ [(CV)n-1 - (CV)n ] mg Pb2+
metal ions, which prevent these to interact with the ( ) = + ( )
g n
g g n-1
adsorbent (Chakraborty and Tare 2006). By
increasing pH, the repulsion becomes weak,
favoring the diffusion of Pb2+ ions to the adsorbent Where C is the remaining concentration of Pb2+ at
surface, which increases adsorption (Jiang, Pang, time t in mg L-1 (calculated with Equation 2), V the
and Liao 2009). volume of the remaining solution at time t in liters,
and n the number of data taken in time t. The graph
of Pb2+ adsorbed as a function of time, allows
identifying the time the equilibrium is reached and
the corresponding adsorption capacity, qe (Acar
and Eren 2006). To assess the rate of Pb2+
adsorption on OC and XC, two kinetic models
were considered. The model of pseudo-first order
was proposed by Lagergren (Tseng, Wu, and
Juang 2010; Lagergren 1898):

k1
log(qe - qt ) = log qe - t
2.303

Where qe and qt are the adsorption capacities (mg

Figure 1. Effect of the exchange solution pH on g-1) at equilibrium and time t (s), respectively, and
Pb2+ adsorption on OC (□) and XC (◊). Adsorbent k1 is the rate constant model (min-1). k1 values are
dose: 50 mg/10 mL, concentration: 100 ppm of obtained from the intercept and slope of the graph
Pb2+, contact time: 3 h. The optimum adsorption of log (qe -qt) vs. t. The kinetic model of pseudo-
pH was 5. second order is given by the equation:
t 1 1
= 2
+ t
Figure 1 shows the maximum adsorption of Pb2+ qt k2 qe qe
on OC and XC at pH 5, with adsorptions of 74% Where qe and qt were defined in the model of
and 99% from solutions of 100 ppm Pb2+ and pseudo-first order, and k2 is the rate constant
doses of 50 mg/10 ml of adsorbent, respectively. model of pseudo-second-order (g mg-1 min-1)
The main advantage of XC over OC is that the (Torres Blancas et al. 2013). k2 and qe values are
adsorption of Pb2+ is higher at all pH values. This obtained from the intercept and slope of the graph
is consistent with reports by Torres-Blancas et al. of t/qt vs. t (Silgado, Marrugo, and Puello 2014).
(2013) who evaluated the adsorption of lead in This model also assumes that the initial rate of
pepper peel and xanthated pepper peel; they adsorption, h0, (mg g-1 min-1) is proportional to the
observed that at low pH, the adsorption on pepper square of the number of remaining free surface
peel was poor as a result of the strong electrostatic sites, defined by:
repulsion, while the adsorption of lead was greater
for xanthated pepper peel in all pH ranges. Similar h0 = k 2 q2e
results have been reported (Orjuela et al. 2000;
Liang, Guo, and Tian 2011; Taty-Costodes et al. Where qe and k2 are the adsorption capacity (mg
2003). g-1) and the pseudo-second order model rate
constant (g mg-1 min-1), respectively. The results
3.2. Adsorption kinetics for each model are described in Table 1.

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Table 1. Kinetic parameters for OC and XC. Pb2+ concentration: 100 ppm, adsorbent dose: 500 mg/100
mL, pH: 5, contact time: 140 min. Adsorbents followed a pseudo second-order kinetics.
Kinetic Model
Pseudo first order Pseudo second order

qe
Adsorbent qe qe k2
(exp) k1
model R2 model (g mg-1 R2 h0 (mg g-1)
min-1
(mg g-1) (mg g-1) min-1)

OC 16.8 16.0 0.031 0.919 17.3 0.018 1.000 5.98

XC 19.8 19.7 0.056 0.901 19.6 0.036 1.000 14.2
qe (exp): experimental qe

From the data, it follows that, for the pseudo-first factor RL given by:
order kinetic model, the theoretical values of qe for 1
𝑅𝐿 =
OC and XC differ from the experimental q e, as 1 + bCo
evidenced by the regression coefficients of 0.919
and 0.901 for OC and XC, respectively, but they Where, b is the Langmuir constant and Co the
agree on the model of pseudo-second order with initial concentration of adsorbate in the solution.
a regression coefficient of 1.00 for both OC and RL indicates the shape of the isotherm and if the
XC. Therefore, the mechanism of adsorption of adsorption is favorable or not, according to: if RL>
lead ions on OC and XC is represented by the 1 it is unfavorable, RL = 1 linear, 0 <RL <1
pseudo-second order kinetic model, and this favorable, and RL = 0 the adsorption is irreversible
agrees with the literature (Torres Blancas et al. (Memon et al. 2007).
2013; Liang et al. 2009; Šćiban, Klašnja, and
Škrbić 2006). This indicates that chemical Unlike the Langmuir isotherm, that assumes a
adsorption was the mechanism of speed control. homogeneous surface, the Freundlich isotherm
As for the initial velocity h0, this was higher for XC considers a heterogeneous surface and is used at
than for OC, confirming that xanthation increased low pressures:
the adsorbent affinity towards metals. 1
Log qe = log KF + Log Ce
n
3.3. Adsorption isotherms
Where qe is the amount of material adsorbed by a
Adsorption isotherms are mathematical models specific amount of adsorbent (mg g-1), Ce the
used to estimate the maximum amount of equilibrium concentration (mg L-1) in the liquid
contaminant that an adsorbent can remove from phase, KF the Freundlich constant (mg1/n L1/n g- 1)
aqueous solution. The adsorption isotherms were and n the heterogeneity factor which depends on
evaluated using the Langmuir and Freundlich the substance (Liang et al. 2009). Figure 2 shows
models. The Langmuir isotherm is given by: the Langmuir and Freundlich isotherms for Pb2+
adsorption and Figure 3 the separation factors for
Ce 1 Ce OC and XC.
= + The isotherms in Figure 2 show that the
qe qm b qm
adsorption capacity in the equilibrium, Ce,
Where qe is the amount of material increases as a function of concentration in
absorbed by a specific amount of adsorbent (mg solution, qe, while Figure 3 confirms that the
g-1), Ce the equilibrium concentration (mg L-1), qm adsorption of Pb2+ on OC and XC was favorable
the amount of metal or contaminant necessary to because the RL values for all metal concentrations
form a monolayer on the adsorbent surface (mg g- were in the range 0 - 1. According to Kumar, Rao,
1
) and expresses its maximum adsorption and Kaul (2000), this means that adsorption is
capacity, and b the Langmuir constant (L mg-1) more favorable at high concentrations. Table 2
(Silgado, Marrugo, and Puello 2014; Šćiban, shows the values of the isotherm parameters for
Klašnja, and Škrbić 2006). The characteristics of OC and XC, determined by least squares.
the Langmuir isotherm can be expressed in terms
of a constant dimension known as the separation

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Figure 2. Langmuir and Freundlich isotherms for Pb2+ adsorption on OC and XC. Adsorbent dose: 50
mg/10 mL, metal concentration: 100 ppm of Pb2+, contact time: 120 min. pH: 5. OC adsorption fits the
Langmuir isotherm and XC a Freundlich type; qe is the adsorption capacity of Pb2+ and Ce the
equilibrium concentration of Pb2+.

Figure 3. Separation Factors (RL) in the adsorption of Pb2+ on OC and XC. Adsorption was favorable
because 0 <RL> 1. Ce is the initial concentration of Pb2+.

Table 2. Langmuir and Freundlich isotherm parameters for Pb2+ adsorption on OC and XC.
Adsorption isotherms
Langmuir Freundlich
Adsorbent
qm, b
R2 RL KF, L g-1 n R2
mg g-1 L mg-1
OC 10.4 0.416 0.97 0.035 1.042 0.39 0.914
XC 60.1 0.025 0.53 0.32 96.39 0.68 0.981
qm: amount of metal or contaminant necessary to form a monolayer on the adsorbent surface (mg g -1. b: Langmuir
constant (L mg-1). R: correlation coefficient. RL: separation factor. KF: Freundlich constant (mg1/n L1/n g- 1).

To determine which of the two isotherm models which formed a monolayer, wherein each
was best suited to Pb2+ adsorption, we evaluated adsorption site may adhere a single adsorbate
correlation coefficients that measure how well the molecule, and they have the same adsorption
experimental values were adjusted to theoretical energy. Our results also partially agree with Liang
ones (Pillai et al. 2013; Panda, Das, and Guha et al. (2009), who studied the adsorption of lead on
2008). Table 2 shows that the correlation untreated orange peel, and concluded that it
coefficients with respect to lead adsorption on OC follows a Freundlich isotherm type, but once
were 0.971 and 0.914, and for XC, 0.53 and 0.981, xanthated follows a Langmuir type. On the other
for the Langmuir and Freundlich models, hand, Torres-Blancas et al. (2013) established
respectively. This means that for OC and XC the that the adsorption of lead on xanthated and
best fits are given by the Langmuir and Freundlich untreated pepper peel follows a Freundlich
models, respectively. That is, in XC, lead isotherm type. This means that the type of
adsorption occurred due to the energy distribution isotherm depends on the nature of adsorbent
of the active sites for adsorption and the absence used. Thermodynamically, when the adsorption
of monolayers and, in OC, the Pb2+ adsorption was kinetic model is of pseudo second order, the
given on a surface of homogeneous adsorbent system seeks its lower energy state by finding its

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equilibrium, a typical behavior for pseudo-second associations such as alcohols and phenols (Torres
order mechanisms. This is, the activation energy Blancas et al. 2013), and at 2920 cm-1 due to CH
between the solid surface and the adsorbed lead groups stretching vibration produced by alkanes
ion reaches its maximum value when the number and -OCH3 and -CH2OH groups, in the structure of
of the interactions between them manages to coal (Liang, Guo, and Tian 2011). The peak at
generate the value of that energy. 1696 cm-1 was the result of stretching vibrations of
carbonyl groups in coal. The peaks at 1648, 1616,
3.4. Infrared spectroscopy 1560, 1542, 1510, 1456, 1431 and 1423 cm-1 were
due to stretching vibrations of C = C bonds of
The FTIR spectra of OC and XC are shown in aromatic groups in coal. The peaks at 1313, 1338,
Figure 4. In the spectrum of OC, broad, intense 1190, 1167 and 1114 cm-1 were assigned to
absorption peaks around 3442 cm-1 correspond to torsion or deformation and O-H stretching
OH stretching vibrations due to inter and intra vibrations of C-O of primary and secondary
macromolecular hydrogen bonds of molecular alcohols, and phenolic groups.

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Figure 4. FTIR spectra of OC (above) and XC (below)

Some changes were observed in the spectrum of This is consistent with reports by Panda, Das, and
XC with respect to OC. For example, the peaks Guha 2008), who identified xanthate groups in
due to stretching vibrations of OH, CH2 and CH3 Lathyrus Sativus peel, a legume from Asia and
groups are weaker and more elongated than in OC East Africa, by peaks appearing at 661, 1080,
because hydroxyl groups reacted with CS2. 1163 and from 1200 to 1250 cm-1; Pillai et al.
Xanthate groups in XC have been identified by the (2013) who associated sulfur groups to peaks at
appearance of new peaks at 610 and 1034 cm-1 538, 1020 and 1151 cm-1 corresponding to γC-S,
- γC=S y γ S-C-S vibrations; and Mustafa, Hamid,

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and Naeem (2004), who indicated that xanthate such as temperature, adsorbent dose, Pb2+
groups were found at 800-1200 cm-1. solution concentration and volume, adsorption
time, and adsorption experiment set-up such as
3.5. Comparison with other adsorbents passing the solution through a column filled with
the adsorbent or stirring a mixture lead-adsorbent
The present results were compared with data on etc. However, the adsorption capacity of our
lead adsorption from the literature (Table 3). The adsorbent was comparable to those of other
comparison of the different experiments in Table 3 experiments (Simonova et al. 2010).
is difficult because they used different conditions

Table 3. Comparison of Pb2+adsorption with data from other adsorbents in the literature.
Location Adsorption
Coal type Kinetics Model Reference
capacity
El Cerrejon, Pseudo
Subbituminous Langmuir 10.4 mg g-1 This work
Colombia second order
Xanthated El Cerrejon, Pseudo
Freundlich 60 mg g-1 a This work
Subbituminous Colombia second order
Activated Lakhra, Pseudo first Bhutto and
Langmuir 758 ± 8 mg g−1 b
Lignite Pakistan order Khan 2012
Lakhra, Pseudo first Bhutto and
Lignite Langmuir 2-3 mg g−1 b
Pakistan order Khan 2012
Alkali-activated Aleksandriisk Simonova et
First order Freundlich 54-170 mg g−1 c
Brown coal Ukraine al. 2010
Activated
Yi et al. 2016
carbon from China d First order Langmuir 162 mg g-1
coal
a
50 mg of adsorbent with 10 mL of Pb2+ at 25-400 g L-1; b 28°C; the effluent was passed through a
column of 0.9 cm I.D. with 1.49 g cm-3 packing density, with 2.0 g of adsorbent; c 20°C, Initial
concentration of lead, С0 = 0.2– 20 g L-1; d from Guoqing Water Purification Material Co. Ltd. 100 mL of
Pb(II) solution; 0°C; 20°C; 20°C; 20°C; 20°C.
014
4. Conclusions
2. Bhutto, S.; M. N. Khan; The use of
Swelled xanthated coal has a great potential as an indigenous coal reserves for the removal
efficient adsorbent. Its adsorption capacity of Pb2+ of lead (II) from the aquatic environment
was 60 mg Pb2+ g-1, following a Freundlich type by adsorption. Int. J. Environ. Stud. 2012,
isotherm. The optimal pH for adsorption was ≥ 5 69, 888.
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the adsorption equilibrium was reached in about 8316
120 minutes following a pseudo-second order
kinetics. FTIR spectra showed the incorporation of 3. Chakraborty, S.; V. Tare; Role of various
xanthate groups in the chemical structure of coal. parameters in synthesis of insoluble
The introduction of xanthate groups were agrobased xanthates for removal of copper
responsible for the high metal adsorption of the from wastewater. Biores. Technol. 2006,
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Graphical Abstract

Highlights
 We describe lead adsorption by xanthate-
modified coal (treatment with CS2 and
NaOH)
 The best lead adsorption was at pH 5
(98%)
 Equilibrium reached at 120 min followed
pseudo-second order kinetics suited to
Freundlich isotherm

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 SUPPLEMENTARY MATERIAL

0.5
0

log (qe - qt ) (mg Pb2+ g-1 CX)

0 50 100 150 0
log (qe - qt ) (mg Pb2+ g-1 C)

-0.5 -0.5 0 50 100 150

-1 -1
y = -0.0244x + 0.2336
y = -0.0186x - 0.1721 -1.5 R² = 0.9007
-1.5
R² = 0.9186 -2
-2
-2.5
-2.5 -3
-3.5
-3 time (min)
-3.5
time (min)
Figure S3. Pseudo first order kinetic model for
Figure S1. Pseudo first order kinetic model for XC. Metal concentration: 100 ppm of Pb2+,
OC. Metal concentration: 100 ppm of Pb2+, adsorbent dose: 500 mg/100 mL, pH 5, contact
adsorbent dose: 500 mg/100 mL, pH 5, contact time: 140 min.
time: 140 min.

8
9
g-1 CX)

7
8
t/qt ( min/ mg Pb2+ g-1 C)

6
7
Pb2+

5
6
4
t/qt ( min/ mg

5
3 y = 0.0501x + 0.0361
4 R² = 1
2
3 y = 0.0596x + 0.0179
R² = 1 1
2
0
1 0 50 100 150
0 time (min)
0 50 100 150
Time (min) Figure S4. Pseudo second-order kinetic model for
XC. Metal concentration: 100 ppm of Pb2+,
Figure S2. Pseudo second-order kinetic model for adsorbent dose: 500 mg/100 mL, pH 5, contact
OC. Metal concentration: 100 ppm of Pb2+, time: 140 min.
adsorbent dose: 500 mg/100 mL, pH 5, contact
time: 140 min. Figures S1 and S3 correspond to the liberalization
of the pseudo-first order model, while figures S2
and S4 to the pseudo-second order model. The
graphs show that the experimental results best fit
the pseudo-second order model for both materials,
and this means that chemical adsorption was the
mechanism of speed control.

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