Orbital: The Electronic Journal of Chemistry

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ISSN 1984-6428
 Vol 5   No. 3   Special Issue 2013 
Full Paper

Adsorption of Crystal Violet Dye from Aqueous Solution onto

Zeolites from Coal Fly and Bottom Ashes
Tharcila C. R. Bertolini*, Juliana C. Izidoro, Carina P. Magdalena, Denise A. Fungaro

Chemical and Environmental Center, Nuclear and Energy Research Institute, Av. Prof. Lineu Prestes, 2242,
CEP 05508-000, São Paulo, Brazil.

Article history: Received: 27 March 2013; revised: 05 June 2013; accepted: 22 July 2013. Available online: 10 October
2013.

Abstract: The adsorption of the cationic dye Crystal Violet (CV) over zeolites from coal fly ash (ZFA) and
bottom ash (ZBA) was evaluated. The coal fly ash (CFA) and the coal bottom ash (CBA) used in the
synthesis of the zeolites by alkaline hydrothermal treatment were collected in Jorge Lacerda coal-fired power
plant located at Capivari de Baixo County, in Santa Catarina State, Brazil. The zeolitic materials were
characterized predominantly as hydroxy-sodalite and NaX. The dye adsorption equilibrium was reached after
10 min for ZFA and ZBA. The kinetics studies indicated that the adsorption followed the pseudo-second
order kinetics and that surface adsorption and intraparticle diffusion were involved in the adsorption
mechanism for both the adsorbents. The equilibrium data of ZFA was found to best fit to the Langmuir
model, while ZBA was best explained by the Freundlich model. The maximum adsorption capacities were
19.6 mg g-1 for the CV/ZFA and 17.6 mg g-1 for the CV/ZBA.

Keywords: crystal violet; coal fly ash; coal bottom ash; zeolite; adsorption

1. INTRODUCTION inhalation and ingestion. In extreme cases, can lead to

kidney failure, severe eye irritation leading to
The manufacture and use of synthetic dyes for permanent blindness and cancer [5-6]. Therefore,
dyeing fabrics has become an industry solid. It is removal of this dye from water and wastewater is of
estimated that around 700,000 tons of dyes are great importance.
produced annually around the world. Of this amount
about 20% is unloaded the industrial wastes without Various methods of treatment exploited
previous treatment. However, their use has become a through the years by industries for removing colorants
matter of serious concern to environmentalists. include physicochemical, chemical, and biological
Synthetic dyes are highly toxic causing negative methods, such as flocculation, coagulation,
effects on all life forms because they present sulfur, precipitation, adsorption, membrane filtration,
naphthol, vat dyes, nitrates, acetic acid, surfactants, electrochemical techniques, ozonation, and fungal
enzymes chromium compounds and metals such as decolorization [7]. However, due to the fact that
copper, arsenic, lead, cadmium, mercury, nickel, effluents contain different dyes, and these dyes
cobalt and certain auxiliary chemicals [1-2]. contain complex structures, is very difficult to treat
using conventional methods [8].
The crystal violet (CV) dye is a synthetic
cationic dye and transmits violet color in aqueous The adsorption is one of the most effective
solution. It is also known as Basic Violet 3, gentian processes of advanced wastewater treatment, which
violet and methyl violet 10B, belonging to the group industries employ to reduce hazardous pollutants
of triarylmethane [3]. This dye is used extensively in present in the effluents. This is a well-known and
the textile industries for dying cotton, wool, silk, superior technique to other processes for removal of
nylon, in manufacture of printing inks and also the dyes from aqueous worldwide due to initial cost,
biological stain, a dermatological agent in veterinary operating conditions and simplicity of design [9].
medicine [3-4]. The CV is toxic and may be absorbed Currently, the most common procedure involves the
through the skin causing irritation and is harmful by use of activated carbon as adsorbent for this purpose

*
Corresponding author. E-mail: thacolachite@yahoo.com.br
 Bertolini et al.
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by offering greater adsorption capacities. However, as a model cationic dye in this work was purchased
due to their relatively high cost, many lower-cost from Proton-Research and considered as purity 100%.
adsorbents have been investigated as adsorbent for The general characteristics of CV are summarized in
removing contaminants from wastewater. The low- Table 1 and the chemical structure is in Fig. 1. A
cost adsorbents can be made from waste materials, stock solution (5.0 g. L-1) was prepared with
thus collaborating with the environment and also deionized water (Millipore Milli-Q) and the solutions
getting economic advantages. A wide variety of low- for adsorption tests were prepared by diluting. The
cost adsorbents have been prepared from different samples of coal fly and bottom ashes were obtained
materials utilizing industrial, biomass, and municipal from Jorge Lacerda coal-fired power plant located at
wastes [10-14]. Capivari de Baixo County, in Santa Catarina State,
Brazil.
Thermoelectric power stations produce a great
quantity of residues from combustion of coal. The Table 1. General characteristics of CV dye.
major solid waste by-product of thermal power plants Chemical name Crystal Violet
based on coal burning is fly ash. The coal-fired power Color index CI 42555
λmax (nm) 590
plants in the southern of Brazil produce Molar mass (g mol-1) 408
approximately 4 Mt of ash per year, of which 65–85% Chemical formula C25H30N3Cl
is fly ash and 15–35% bottom ash. The main uses of
fly ash include pozzolanic cement, paving, bricks,
etc., but only 30% of what is produced in the year are CH3 CH3

recycled [15-16]. The bottom ash are previously

N N
disaggregated and transported to the settling ponds H3C CH3
through pumping hydraulic [17]. This may lead to Cl
environmental problems through leaching of toxic
substances present in the ashes. One way to reduce
the environmental impact of the disposal of these
wastes is to expand its utilization. An alternative solid
waste is recycling of the transformation of the coal
ash at a low cost adsorbent able to remove toxic
substances from contaminated waters [18-22].
N
The coal ash can be converted into zeolites due H3C CH3
to their high contents of silicon and aluminum, which Figure 1. Chemical Structure of CV.
are the structural elements of zeolites. The most
common method involves a hydrothermal treatment
with sodium hydroxide [23-24]. This technique of Zeolite synthesis
recycling coal ashes has been extensively investigated The zeolite was synthesized by hydrothermal
for water treatment due to its large specific surface activation of 20 g of coal fly (CFA) or coal bottom
area and cation exchange capacity, low cost, and ashes (CBA) at 100 °C in 160 mL of 3.5 mol L-1
mechanical strength [25-29]. NaOH solution for 24 h. The zeolitic material was
The aim of this work was to evaluate the repeatedly washed with deionized water to remove
efficiency of synthesized zeolites from Brazilian coal excess sodium hydroxide until the washing water had
fly and bottom ashes as adsorbent in the removal of pH ~ 10, then it was dried at 50 °C for 12 h [30]. The
basic dye crystal violet from aqueous solutions. Batch zeolitic products obtained were labeled as ZFA and
kinetic experiments were performed to provide ZBA for zeolite prepared with fly ash and bottom ash,
appropriate equilibrium times. The Langmuir and respectively.
Freundlich isotherm models were used to model the
isotherm data for their applicability.
Adsorbents characterization
The mineralogical compositions of the samples
2. MATERIAL AND METHODS (ZFA and ZBA) used as adsorbents and the samples
All chemicals used in this study were of saturated with dye (CV/ZFA and CV/ZBA) were
analytical grade. Crystal Violet (CV) which was used determined by X-ray diffraction analyses (XRD) with

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an automated Rigaku multiflex diffractometer with at 1050°C for 4 h in a muffle furnace and expressed in
Cu anode using Co Kα radiation at 40 kV and 20 mA percentage. The mass of the material used was 0.5 g.
over the range (2θ) of 5–80°with a scan time of
The chemical composition and the some
0.5°/min.
physicochemical properties (bulk density, BET area,
The chemical composition of CBA and ZBA, total and cation exchange capacity, pH) of CFA and
in the form of major oxides, was determined by X-ray ZFA have been described in a previous paper [26].
fluorescence (XRF) in a Rigaku RIX- 3000
equipment. The bulk density and the specific surface
area of CBA and ZBA was determined by a helium Adsorption studies
picnometer (Micromeritcs Instrument Corporation — The adsorption was performed using the batch
Accupyc 1330) and by a BET Surface Area Analyser procedure. Kinetic experiments were carried out by
(Quantachrome Nova — 1200), respectively. Prior to agitating 0.25 g of adsorbent with 25 mL of dye
determination of the specific surface area, samples solution with initial concentration of 185 mg L-1 at
were heated at 423.15 K for 12 h to remove volatiles room temperature (25 ± 2 °C) at 120 rpm for 1-12 min
and moisture in a degasser (Nova 1000 Degasser). for both adsorbents. The collected samples were then
The BET surface areas were obtained by applying the centrifuged (3000 rpm during 30 min for ZFA and
BET equation to the nitrogen adsorption data. during 10 min for ZBA) and the concentration in the
For the cation exchange capacity (CEC) supernatant solution was analyzed using a UV
measurements, the samples CBA and ZBA were spectrophotometer (Cary 1E, Varian) by measuring
saturated with sodium acetate solution (1 mol L-1), absorbance at λ = 590 nm and pH = 5.
washed with 1L of distilled water and then mixed The adsorption capacity (mg·g-1) of adsorbents
with ammonium acetate solution (1 mol L-1) [31]. The was calculated using Eq. 1:
sodium ion concentration of the resulting solution was
determined by optical emission spectrometry with V (Co  C f )
inductively coupled plasma — ICP-OES q (1)
M
(Spedtroflame — M120).
where q is the adsorbed amount of dye per gram of
The pH and the conductivity were measured as
adsorbent, C0 and Cf the concentrations of the dye in
follows: the bottom ashes and zeolite bottom ashes
the initial solution and equilibrium, respectively (mg
(0.25 g) were placed in 25 mL of deionized water and
L-1); V the volume of the dye solution added (L) and
the mixture was stirred for 24 h in a shaker at 120 rpm
M the amount of the adsorbent used (g).
(Ética — Mod 430). After filtration, the pH of the
solutions was measured with a pH meter The efficiency of adsorption (or
(MSTecnopon — Mod MPA 210) and the removal) was calculated using the equation:
conductivity was measured with a conductivimeter
(Co  C f )
(BEL Engineering - Mod W12D). R  100 (2)
Co
The determination of the zero point charge
(pHPZC) of ZFA and ZBA was carried out as follows: where R is the efficiency of adsorption (%), Co is the
the samples (0.1 g) were placed in 50 mL of initial concentration of dye (mg L-1), Cf is the
potassium nitrate (0.1 mol L-1) and the equilibrium concentration of dye at time t (mg L-1).
mixtures were stirred for 24 h in the mechanical
Adsorption isotherms were carried out by
stirrer (Quimis – MOD Q-225M) at 120 rpm. The
agitating 0.25 g of zeolite with 25 mL of crystal violet
initial pH of solutions was adjusted to the values of 2,
over the concentration ranging from 24.4 to 236 mg
4, 10, 11, 12 and 13 by addition of 0.1 and 1 mol L-1
L-1 for ZFA and 24.4 to 247.9 mg L-1 for ZBA till the
HCl or 3 mol L-1 NaOH solution. The difference
equilibrium was achieved. The adsorption capacity
values between the initial and final pH (pH Δ) were
(mg g-1) of adsorbents was calculated using a Eq.1.
placed in a graph in function of the initial pH. The
point x where the curve intersects the y = 0 is the pH
of PCZ.
3. RESULTS AND DISCUSSION
The content of loss of ignition (LOI) of coal
Characterization of the adsorbents material
bottom ashes in this study were calculated according
to the weight loss of the samples subjected to heating The X-ray diffractograms of ZFA and ZBA are

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shown in Fig. 2 and 3, respectively. The identification NaX (JCPDS 38-0237) with peaks of quartz (JCPDS
and interpretation of PXRD patterns of the materials 85-0796) and mullite (JCPDS 74–4143) of ashes that
are prepared by comparing the diffraction database remained after the treatment. The mineralogical
provided by “International Centre for Diffraction composition of ash used as raw material for the
Data/Joint Committee on Power Diffraction synthesis of zeolites depends on the geological factors
Standards” (ICDD/JCPDS). The phases in zeolitic related to the formation and deposition of coal and its
materials were hydroxysodalite (JCPDS 31-1271) and combustion conditions.

X
Q

ZFA
1200 H

M M
H
Intensity

800
X
H Q
H H M
MX M
Q Q
400 X X H H
H X M M H
Q
M
H
QQ H M M
QH Q H Q Q
X M Q
X M

0
0 10 20 30 40 50 60 70 80
2Theta (°)

Figure 2. XRD Patterns of ZFA (Q = Quartz, M = Mullite, H = Hydroxysodalite zeolite, X = NaX zeolite).

X
2000 Q

ZBA
1600

1200
Intensity

Q MM

800 M H
H
M M
H H Q
X H H
XH H
400 X M M Q H
Q Q QM
H H X Q
M
Q Q
X
X X

0
0 10 20 30 40 50 60 70 80 90
2Theta (°)

Figure 3. XRD Patterns of ZBA (Q = Quartz, M = Mullite, H = Hydroxysodalite zeolite, X = NaX zeolite).

adsorption of molecules CV.

The diffraction patterns of the zeolites
obtained before and after adsorption of CV are shown The chemical composition of CBA and ZBA
in Fig. 4. The structural parameters of saturated ZFA determined by X-ray fluorescence (XFR) is shown in
and ZBA were very close to those of the Table 2. The chemical compositions of CFA and ZFA
corresponding ZFA and ZBA before adsorption. The have been described in detail in previous paper [26].
crystalline nature of the zeolites remained intact after

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Intensity ZBA/CV

ZBA

X ZFA/CV
Q H
H M H M
H MQ
X QM H H
X Q H M M
X H M H M
X QM
ZFA

0 10 20 30 40 50 60 70 80
2 Theta (°)

Figure 4. XRD Patterns of zeolites and zeolites saturated with dye (Q = Quartz, M = Mullite, H = Hydroxy-
sodalite zeolite, X = NaX zeolite).

bituminous-type, highly volatile (C/A). Samples of fly

Table 2. Chemical composition of CBA and ZBA.
Elements (wt. %) CBA ZBA ash showed the following ranges of the main elements
SiO2 49.6 35.1 of higher concentration (wt.%): 57.98 – 60.10 of
Al2O3 27 32.9 SiO2, 22.98-26.97 of Al2O3 and 4.67-8.01 of Fe2O3.
Fe2O3 10.9 16.1 For samples of bottom ash ranges were (wt.%): 46.14
Na2O 1.9 7.7
CaO 1.8 3.2 to 61.95 of SiO2, 19.20 to 23.88 of Al2O3 and 5.38 to
K2O 4.4 0.7 7.81 of Fe2O3.
TiO2 1.9 2.4
SO3 0.7 0.3 The chemical composition found for ZBA is
MgO 1.3 1.3 mainly silica, alumina, iron oxide and sodium oxide
ZnO 0.03 0.03 (Table 2). The main constituents for ZFA were 36.6
ZrO2 0.03 0.04
SiO2/ Al2O3 1.84 1.06
wt.% of SiO2, 38.0 wt.% of Al2O3, 8.30 wt.% of
Fe2O3 and 6,90 wt.% of Na2O. A significant amount
of Na element is incorporated in the final products
The main constituents of CBA are silica due to hydrothermal treatment with NaOH solution.
(SiO2), alumina (Al2O3), and ferric oxide (Fe2O3).
Quantities below 5 wt.% of K2O, CaO, TiO2, SO3 and The SiO2/Al2O3 ratio for zeolites is associated
MgO are also observed. to the cation exchange capacity. The values observed
for ZFA was 0.96 and the value calculated for ZBA
The main constituents observed for CBA were was 1.06 (Table 2). The SiO2/Al2O3 ratios for the
the same of CFA: 50.3 wt.% of SiO2, 29.8 wt.% of zeolites are lower than the values of raw fly and
Al2O3, and 6.70 wt.% of Fe2O3. It has found also bottom ashes. The hydrothermal treatment contributed
oxides of calcium, titanium, sulfur and other to the increase in the cation exchange capacity of
compounds in amounts below 5 wt.%. The these materials. The zeolitic material that exhibit
SiO2/Al2O3 ratio was 1.69 and 1.84 for CFA and lower the ratio SiO2/Al2O3, have higher the cation
CBA, respectively, indicating good source to exchange capacity.
synthesize zeolites [32].
Some physicochemical properties of coal
The coal and its ash generated in Jorge bottom ash and its zeolitic material are given in Table
Lacerda coal-fired power plant were analyzed by 3. The same physicochemical properties for CFA and
Silva et al 2010. The results indicated that coal is ZFA are presented in previous paper [26].

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Table 3. Physicochemical properties of coal bottom the present study.

ash (CBA) and zeolite from coal bottom ash (ZBA).
Properties physicochemical CBA ZBA The point of zero charge (PZC) is defined as
Bulk density (g cm-3) 1.79 2.43 the pH at which the surface of the adsorbent has
BET surface area (m2 g-1) 5.33 84.9 neutral charge. The pHPCZ adsorbents depends on
Loss of ignition (%) 9.33 - several factors such as the nature of crystallinity,
pH in water 7.6 8.4 Si/Al ratio, impurity content, temperature, adsorption
pHPZCa - 7.3 efficiency of electrolytes, degree of adsorption of H+
Condutivity (µS cm-1) 110 367 and OH-, and, therefore, it must vary adsorbent for
CEC (meq g-1)b 0.109 1.19 adsorbing [37]. The value of pHPZC of ZBA (Table 3)
(a) point of zero charge; (b) cation exchange capacity was lower than the pH in water indicating that the
surface presented negative charge in aqueous solution
The bulk density values ranged from 1.79 to (pH> pHPCZ). The value of the pHPZC of ZFA obtained
2.43 g cm-3 for ash and zeolites. Kreuz [33] found in this study was 6.5. This value is lower than the pH
value of bulk density 1.81 g cm-3 for bottom ash from and the surface of ZFA also showed negative charge.
thermal power plant Jorge Lacerda, which is very
The data of loss on ignition of coal ash may
close to the value found for the ash of this study.
indicate the combustion efficiency of a thermoelectric
The specific surface area value of the zeolite power plant. The high levels of this property make it
bottom ash was approximately 16 times greater than difficult the synthesis of zeolites, as the non-reactive
those of its precursor ash. The specific surface area phase may be a lesser amount during conversion. The
value for ZFA was also higher (134.3 m2 g-1) than the loss on ignition is usually indicative of the presence of
value for CFA (9.6 m2 g-1). This area increase is due unburned carbon and mineral phases stable at high
to the crystallization stage zeolitic on the smooth temperatures [38]. The loss on ignition values found
spherical particles of the ash after the hydrothermal for CFA and CBA were 15.1% and 9.33%,
treatment. respectively. According to the obtained values of loss
The CEC values of the ash are much low, and on ignition of Brazilian fly ash was suggested that the
is similar to the value reported in the literature [34]. Jorge Lacerda Thermal Power Plant has a low
The CEC values of ZBA and ZFA were 10 and 50 efficiency [26].
times higher than CBA and CFA, respectively, due to
hydrothermal treatment. Therefore, the synthesized
Kinetics studies
zeolites can be used as good cation exchanger.
Figure 5 shows the effect of contact time on
The pH of the coal ash is directly related to the
adsorption process of CV on ZFA and on ZBA. The
availability of macro and micro nutrient and indicates
efficiency of dye removal was increased as the
whether coal ash is acidic or alkaline in nature. Based
agitation time increased until equilibrium. The
on the pH, coal ash has been classified into 3
adsorption equilibrium with ZFA and ZBA were
categories, namely; slightly alkaline 6.5–7.5;
reached at 10 min. The process shows the removal of
moderately alkaline 7.5-8.5 and highly alkaline >8.5
71% and 50% with ZFA e ZBA, respectively.
[35]. The pH values of fly ash (8.0) and bottom ash
(7.6) indicates that ashes were moderately alkaline in
20
nature. This alkalinity is justified by the presence of
compounds formed by the cations K+, Na+, Ca2+ and 16
ZFA
ZBA

Mg2+ combined with carbonates, oxides or hydroxides

[34]. The pH of zeolitic materials increased due to 12
q (mg g )
-1

hydrothermal treatment with NaOH solution. 8

The conductivity values found for synthesized

4
zeolites were higher than those of raw ashes. This
increase is explained by presence of exchangeable 0
0 4 8 12
cations in the structures of the zeolites formed by the t (min)

hydrothermal treatment. Figure 5. Effect of contact time on the adsorption of

Depoi et al. [36] found a conductivity value of CV onto ZFA and ZBA.
119 μS cm-1 for bottom ash, which is accordance with Kinetic models

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In order to investigate the adsorption processes dq

 k 2 dt (6)
of CV onto adsorbents, pseudo-first order and pseudo- ( qe  q ) 2
second order kinetic models were applied to the
experimental data. The pseudo-first-order kinetic Integrating Eq. (6) for the boundary conditions t = 0
model, proposed by Lagergren, has been widely used to t = t and q = 0 to q = q gives
to predict the dye adsorption kinetics. The dye
t 1 1
adsorption kinetics following the pseudo-first-order  2
 t (7)
q k 2 qe qe
model is given by [39]:

dq A plot of t/q vs. t gives the value of the

 k 1( qe  q ) (3) constants k2 (g mg-1 min-1), and also qe (mg g-1) can be
dt
calculated.
where q and qe represent the amount of dye adsorbed
Because the above two equations cannot give
(mg g-1) at any time t and at equilibrium time,
definite mechanisms, the intraparticle diffusion model
respectively, and k1 represents the adsorption rate
was tested. According to Weber and Morris [41], an
constant (min-1). Integrating Eq. (3) with respect to
intraparticle diffusion coefficient kdif is defined by the
boundary conditions q = 0 at t = 0 and q = q at t = t,
equation:
then Eq. (3) becomes:

log10 (qe – q) = log10qe – k1 t /2,303 (4)

qt = kdif t½ + C (8)
where kdif is the intraparticle diffusion rate constant
Thus the rate constant k1 (min-1) can be
(mg g-1 min-1/2), and C is the intraparticle diffusion
calculated from the plot of log (qe-q) vs. time t.
constant (mg g-1). The constants kdif and C can be
The kinetic data were further analyzed using a obtained, respectively, from the slope and intercept of
pseudo second- order relation proposed by [40] which the plot of qt versus t1/2. The relative values of C give
is represented by: an idea about the boundary layer thickness, i.e., the
larger the intercept value, the greater the boundary
dq
 k 2 ( qe  q ) 2 (5) layer effect [41-43].
dt
Figure 6 shows the fitting results using (a)
where k2 is the pseudo-second-order rate constant (g
first-order kinetic model; (b) second-order kinetic
mg-1 min-1) and qe and q represent the amount of dye
model, and (c) diffusion model. The parameters for all
adsorbed (mg g-1) at equilibrium and at any time t.
models are presented in Table 4.
Separating the variables in Eq. (6) gives

1.0
(a) (b)
1.2

0.5
ZFA
ZBA 0.8
Log qe-q

0.0
t/q

0.4 ZFA
-0.5 ZBA

-1.0 0.0
0 4 8 12 0 4 8 12
t (min) t (min)

15 (c)

12

9
q (mg g )
-1

ZFA
3 ZBA

0
0 1 2 3 4
0.5 0.5
t (min)

Figure 6. Comparison of kinetic models, and diffusion model of CV adsorption on ZFA and ZBA (a) first-order
kinetics; (b) second-order kinetics; (c) diffusion model.

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Table 4. Kinetic parameters for CV removal onto ZFA and ZBA.

Adsorbents Pseudo- first order
k1 qe calc qe exp (mg g-1) R1
(min) -1 (mg g-1)
ZFA 3.17 x 10-1 9.10 12.8 0.927
ZBA 2.99 x 10-1 7.16 9.11 0.970
Pseudo- second order
k2 h (mg g-1min-1) qe calc (mg g-1) qe exp (mg g-1) R2
(gmg min-1)
-1

ZFA 5.59 x 10-2 10.8 13.9 12.8 0.996

ZBA 5.60 x 10-2 5.88 10.2 9.11 0.995
Intraparticle diffusion
C kdif Ri
(mg g-1min-0.5)
ZFA 5.49 2.17 0.986
ZBA 2.92 1.85 0.995

The experimental qe values (Table 4) did not to the presence of intraparticle diffusion in the system.
agree with the calculated ones obtained from the However, the fact that the lines do not pass through
linear plots, indicating that the pseudo-first order the origin of the plots indicates that, although
model does not reproduce the adsorption kinetics of intraparticle diffusion may be involved in the
CV onto ZFA and ZBA. The k2 and qe determined adsorption process, it was not the rate-controlling step
from the model are presented in Table 4 along with [41].
the corresponding correlation coefficients. The values
A comparison of calculated and measurement
of the calculated and experimental qe are close to ZFA
results for kinetic of CV adsorption onto ZFA and
and also to ZBA, and the calculated correlation
ZBA are shown in Fig. 7a and 7b, respectively. As
coefficients (R) are also very close to unity. Hence,
can be seen, the pseudo-first order model
the pseudo-second order model better represented the
underestimates the adsorption and the pseudo second-
adsorption kinetics.
order kinetic model provides the best correlation for
The linearity of the fitting lines obtained from both adsorption processes.
the application of the diffusion model (Fig. 6c) points

(a) 9 (b)
12

8 6
q (mg g )

q (mg g )
-1

-1

Experimental Experimental
4 Pseudo 1st order 3 Pseudo 1st order
Pseudo 2nd order Pseudo 2nd order
Intraparticle diffusion Intraparticle diffusion

0 0
0 4 8 12 0 3 6 9 12
t (min) t (min)

Figure 7. Comparison between the measured and modeled time profiles for adsorption of CV for (a) ZFA and
(b) ZBA.

Adsorption equilibrium quantity qe is the amount of solute adsorbed per unit

weight of the solid adsorbent, and Ce is the
In adsorption in a solid–liquid system, the
concentration of solute remaining in the solution at
distribution ratio of the solute between the liquid and
equilibrium.
the solid phases is a measure of the position of
equilibrium. The preferred form of depicting this The analysis of the isotherm data is important
distribution is to express the quantity qe as a function to develop an equation which accurately represents
of Ce at a fixed temperature and an expression of this the results and which could be used for design
type is termed an adsorption isotherm [44]. The purposes [39]. In the present study, Langmuir,

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Freundlich and Dubinin-Radushkevich (D-R) models where, Ce is the equilibrium concentration of

were used to describe the equilibrium data. adsorbate in solution (mol L-1), R is the gas constant
(J mol-1 K-1) and T is the absolute temperature (K).
The Langmuir isotherm assumes that the
The D-R model constants, KDR and β, can be
sorption takes place at specific homogeneous sites
determined from the intercept and slope of linear plot
within the adsorbent [45]. The linear form of
of ln qe versus Є2, respectively.
Langmuir isotherm is represented by the Eq. 9:
The constant β gives an idea about the mean
Ce 1 C
  e (9) free energy E (kJ mol-1) of adsorption per molecule of
qe Qob Qo the adsorbate when it is transferred to the surface of
where Ce is the equilibrium concentration (mg L-1), qe the solid from infinity in the solution and can be
the amount adsorbed at equilibrium (mg g-1), Q0 the calculated from the relationship:
adsorption capacity (mg g-1) and, b is the energy of 1
E=
adsorption (Langmuir constant, L mg-1). The values of -2 (13)
Q0 and b were calculated from the slope and intercept
of the linear plots Ce qe-1 versus Ce which give a If the magnitude of E is between 8 and 16 kJ
-1
straight line of slope 1/Q0 that corresponds to mol , the adsorption process is supposed to proceed
complete monolayer coverage (mg g-1) and the via ion-exchange or chemisorption, while for values
intercept is 1/Q0b. of E<8 kJmol-1, the adsorption process is of physical
nature [48].
The Freundlich isotherm is derived by
assuming a heterogeneous surface with a non-uniform Figures 8 and 9 show the adsorption isotherms
distribution of heat of adsorption over the surface of CV on ZFA and ZBA, respectively, where the
[46]. The logarithmic form is shown as Eq. 10: experimental values and curves achieved from the
values estimated by the Langmuir, Freundlich and D-
1 R models are presented. The adsorption efficiency
log qe = log Kf + log Ce (10)
n was between 78 to 99% ZFA and 65 to 96% for ZBA
where KF [(mg g-1 (L mg-1)1/n)] and n are the at equilibrium time.
Freundlich constants related to adsorption capacity Giles et al. [49] state that isotherm shapes are
and adsorption intensity of adsorbents, respectively. largely determined by the adsorption mechanism, and
They were calculated from the intercept and slope of thus can be used to explain the nature of adsorption.
the plot log qe versus log Ce. The adsorption isotherm for solution may be
Langmuir and Freundlich isotherms do not classified into four main classes relating to their
give any idea about adsorption mechanism. The shapes termed S, L, H and C and subgroups 1, 2, 3, 4
Dubinin–Radushkevich isotherm (D-R) is generally or max. The equilibrium isotherms for the system
applied to express the adsorption mechanism CV/ZFA showed sigmoidal curve in the class with the
(physical or chemical) with a Gaussian energy corresponding behavior L2. In processes where such
distribution onto a heterogeneous surface [47]. This isotherms are obtained, the adsorption of solute onto
isotherm model is more general than Langmuir the adsorbent proceeds until a monolayer is
isotherm because it does not assume a homogeneous established; the formation of further layers is not
surface or a constant adsorption potential and is possible in this case [50].
related to the porous structure of the adsorbent. The Comparing the isotherm for the system
linear form of D-R isotherm equation is represented CV/ZBA with those given by Giles et al [49], L4 type
as: of isotherm (Langmuir type with two layers) appears
lnqe = ln KDR – β Є2 (11) to fit the adsorption data well. After the first degree of
saturation of the surface, further adsorption takes
where KDR is the theoretical saturation capacity (mol place on new surface.
g-1), β is a constant related to the mean free energy of
adsorption per mole of the adsorbate (mol2 J-2 ), Є is Figures 10 and 11 illustrate the Langmuir,
Polanyi potential which is mathematically represented Freundlich and D-R plots for the removal of CV by
ZFA and ZBA, respectively. The Langmuir,
as: Freundlich, and D-R isotherm constants are given in
ln(1 + 1/Ce) x RT (12)
Table 5 along with the corresponding correlation
coefficients.

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20
24

15

16
qe (mg g )

qe(mg g )
-1

-1
10
Experimental Data
8 Freundlich Experimental Data
Langmuir 5 Freundlich
D-R Langmuir
D-R

0 0
0 20 40 60 0 30 60 90
-1 -1
Ce (mg L ) Ce (mg L )

Figure 8. Adsorption isotherm of CV onto ZFA (T = Figure 9. Adsorption isotherm of CV onto ZBA (T =
25 oC; t agitation = 10 min). 25 oC; t agitation = 10 min).

(a) (b)
3
1.2

2 0.8

log qe
Ce/qe

0.4
1

0.0
0
0 10 20 30 40 50 60 -0.5 0.0 0.5 1.0 1.5 2.0
Ce log Ce

-10 (c)

-11
ln qe

-12

6.00E+008 9.00E+008 1.20E+009

2

Figure 10. Langmuir (a), Freundlich (b) and D-R (c) plots for adsorption of CV onto ZFA.

Table 5. Parameters of the models of Langmuir isotherm, Freundlich and D-R for the CV dye on adsorbents and
values and Chi-square (χ2)
Adsorbents
Lagmuir ZFA ZBA
Qo (mg g-1) 19.6 17.7
B (L mg-1) 0.329 0.0630
R 0.997 0.961
X2 0.706 4.53
Freundlich
KF (mg g-1)(L mg-1)1/n 4.83 2.66
N 2.41 2.53
R 0.959 0.981
X2 4.42 0.869
D-R
β (mol2 J-2) 2.96 x 10-9 3.03 x 10-9
KDR (mol g-1) 2.49 x 10-4 1.39 x 10-4
E (kJ mol-1) 13.0 12.8
R 0.973 0.983
X2 3.01 0.966

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8 1.5
(a)
(b)

6
1.0

log qe
Ce/qe

0.5
2

0 0.0
0 30 60 90 0.0 0.8 1.6 2.4
Ce log Ce

-10 (c)

-11
ln qe

-12

3.00E+008 6.00E+008 9.00E+008

2

Figure 11. Langmuir (a), Freundlich (b) and D-R (c) plots for adsorption of CV onto ZBA.

By comparing the correlation coefficient chemical in nature.

values obtained from the Langmuir, Freundlich and
The non-linear regression Chi-square (X2) test
D-R isotherm models, it can be concluded that the
was employed as a criterion for the fitting quality due
Langmuir isotherm model is more suitable for
to the inherent bias resulting from linearization of
CV/ZFA while the experimental data obtained for
isotherm models. Therefore, it is necessary to analyze
CV/ZBA were fitted well by the Freundlich isotherm
the data set using the Chi-square test to confirm the
model. This may be due to both homogeneous and
best fit isotherm for the adsorption system combined
heterogeneous distribution of active sites on the
with the values of the correlation coefficient. This
surface of the ZBA. Both energy distributions induce
statistical analysis is based on the sum of the squares
single and multilayer adsorption. These might occur
of the differences between the experimental and
simultaneously or subsequently by order of time, both
model calculated data, of which each squared
in a random manner [51].
difference was divided by the corresponding data
The adsorption for the system CV/ZFA obeys obtained by calculating from models [52]. The Chi-
Langmuir isotherm better, indicating predominantly square can be represented by
homogeneous distribution of active sites on the ZFA
surface, since the Langmuir equation assumes that the (qe exp qe calc) 2
χ2 = ∑ (14)
adsorbent surface is energetically homogeneous. qe calc
The Freundlich isotherm constant, n, gives an where qeexp is the equilibrium capacity of the
idea for the favorability of the adsorption process. The adsorbent obtained from experiment (mg·g-1), and
value of n should be less than 10 and higher than qecalc is the equilibrium capacity obtained by
unity for favorable adsorption conditions. As can be calculating from the model (mg·g-1). A low value of
seen from Table 5, the n values for ZFA and ZBA X2 indicates that experimental data fit better to the
were in the range of 1-10, indicating that the value from the model.
adsorption is a favorable process. By evaluating the
D-R isotherm model, the mean adsorption energy, E, Table 5 also shows the values obtained in non-
values were found to be 13.0 kJ mol-1 for ZFA and linear test or Chi-square (X2). The values of
12.8 kJ mol-1 for ZBA, suggesting that the adsorption regression coefficients, R and the linear error
mechanisms of CV onto zeolitic materials are functions, X2, are in agreement to one another. The

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lower value of X2 confirmed statistically a better fit to surface develop negative charges in aqueous solution.
the Langmuir isotherm for the CV/ZFA system and The adsorption of CV on the zeolite of coal ash will
the Freundlich isotherm for the CV/ZBA system. occurs by electrostatic attraction between the
negatively charged sites of the adsorbent and the
The maximum adsorption of capacity of CV,
positively charged dye molecules (=N+(CH3)2) and
according Langmuir, was about 10% higher on the
also by cation exchange.
zeolite ZFA than on the zeolite ZBA, not being a very
significant difference. The result of performance of Table 6 lists a comparison of maximum
the ZFA was expected because this material will have monolayer adsorption capacity of CV on various
particles sizes smaller than the zeolite from coal adsorbents. A close look at the values displayed
botton ash due granulometric characteristics of the ash reveals that the present adsorbents (ZFA and ZBA)
sample that served as raw material. Thus, decreasing have a maximum CV dye uptake value comparable
the particle size increases the externa surface area, with the reported values in some cases. The
which means increasing the number of active sites adsorption capacity varies, and it depends on the
available for adsorption of the adsorbate and thus characteristics of the individual adsorbent and the
increases the efficiency of adsorption [53]. initial concentration of the adsorbate. However, the
present experiments are conducted to find the
Adsorbents like zeolites consist primarily of
technical applicability of the low-cost adsorbents to
silicon and aluminium oxides, whose hydroxylated
treat CV.

Table 6. Comparison of the maximum adsorption of capacities of CV dye onto various adsorbents
Adsorbents Qo (mg g-1) References
Fly ash 74.6 [54]
Bottom ash 12.1 [55]
Sepiolite 77.0 [56]
Sulphuric acid 85.8 [5]
Activated carbon 19.8 [57]
ZFA 19.6 This study
ZBA 17.6 This study

4. CONCLUSION 5. ACKNOWLEDMENTS
The present study showed that is possible to The authors are grateful to Conselho Nacional
convert coal ash into zeolitic materials by alkaline de Desenvolvimento Científico e Tecnológico
hydrothermal treatment. The X-ray diffraction (CNPq), Coordenação de Aperfeiçoamento de Pessoal
analysis demonstrated that hydroxy-sodalite and NaX de Nível Superior (CAPES) for supporting this study
zeolites were formed after the synthesis. These and Jorge Lacerda coal-fired power plant for
zeolites synthesized from fly ash (ZFA) and bottom providing coal ashes samples.
ash (ZBA) are effective adsorbents for removal the
cationic dye crystal violet from aqueous solution. The
pseudo-second order model provides the best 6. REFERENCE AND NOTES
correlation of the experimental data for both [1] Kant, R. Nat. Sci. 2012, 4, 22. [CrossRef]
adsorbents and intraparticle diffusion is involved in [2] Carneiro, P. A.; Pupo Nogueira R. F.; Zanoni, M. V. B.
the adsorption process, but it is not the only rate- Dye. Pigment. 2007, 74, 127. [CrossRef]
limiting step. The equilibrium data fit with the [3] Adak, A.; Bandyopadhyay, M.; Pal, A. Sep. Purif.
Langmuir isotherm for ZFA and the Freundlich Technol. 2005, 44, 139. [CrossRef]
isotherm for ZBA. The adsorption capacity for ZFA [4] Ayed, L.; Chaieb, K.; Cheref, A. World J. Microbiol.
was found to be 19.6 mg g-1 and for ZBA 17.6 mg g-1. Biotechnol. 2009, 25, 705. [CrossRef]

The use of the southern Brazilian coal ash generated [5] Senthilkumaar, S.; Kalaamani, P.; Subburaam, C. V. J.
Hazard. Mater. 2006, 136, 800. [CrossRef]
in power plants for the production of zeolites can
constitute an alternative and noble use for a residue [6] Mittal, A.; Mittal, J.; Malviya, A.; Kaur, D.; Gupta, V. K.
J. Colloid Interface Sci. 2010, 343, 463. [CrossRef]
which has contributed to the degrading of wide areas.
[7] Dabrowski, A. Adv. Coll. Interface Sci. 2001, 93,135.

Orbital: Electron. J. Chem. 5 (3):179-191, 2013

190
 Bertolini et al.
Full Paper
[CrossRef] [34] Paprocki, A. Síntese de zeólitas a partir de cinzas de
carvão visando sua utilização na descontaminação de
[8] Orthman, J.; Zhu, H. Y.; Lu, G. Q. Sep. Purif. Technol. drenagem ácida de mina. [Master’s thesis.] Porto Alegre,
2003, 31, 53. [CrossRef] Brazil, Pontifícia Universidade Católica do Rio Grande do
[9] Fungaro, D. A.; Magdalena, C. P.; Int. J. of Chem. Sul, 2009.
Environ. Eng. Sci. 2012, 3, 74. [35] Sijakova-Ivanova, T.; Panov, Z.; Blazev, K.; Zajkova-
[10] Ahmaruzzaman, M. Adv. Colloid and Interface Sci. 2011, Paneva, V. Int. J. Eng. Sci. Technol. 2011, 3, 8219.
166, 36. [36] Depoi, F. S.; Pozebon, D.; Kalkreuth, W. D. Int. J. Coal
[11] Bhatnagar, A.; Sillanpää, M. Chem. Eng. J. 2010, 157, Geol. 2008, 76, 227. [CrossRef]
277. [CrossRef] [37] Fungaro, D. A.; Borrely, S. I. Ceram. 2012, 58, 77 (in
[12] Gupta V. K.; Carrott, P. J. M.; Ribeiro-Carrot, M. M. L.; Portuguese with English abstract). [CrossRef]
Suhas. Crit. Rev. Environ. Sci. Technol. 2009, 39, 783. [38] Umaña-Peña, J.C. Síntesis de zeolitas a partir de cenizas
[CrossRef] volantes de centrales termoeléctricas de carbón. [PhD
[13] Gupta, V.K.; Suhas J. Environ. Manage. 2009, 90, 2313. Thesis.] Barcelona, Espanha, Universitat Politécnica de
[CrossRef] Catalunya, 2002.

[14] Fungaro, D. A.; Grosche, L. C.; Pinheiro, A. S.; Izidoro, J. [39] Ho, Y. S.; McKay, G. Can. J. Chem. Eng. 1998, 76, 822.
C.; Borrely, S. I. Orbital Elec. J. Chem. 2010, 2, 235. [CrossRef]
[Link] [40] Ho, Y. S.; Wase, D. A. J.; Forstera C.F. Environ. Technol
[15] Levandowski, J.; Kalkreuth, W. Int. J. Coal Geol. 2009, 1996, 17, 71. [CrossRef]
77, 269. [CrossRef] [41] Weber, W. J.; Morris, J. C. Sanit J. Engin. Div., ASCE,
[16] Fungaro, D. A.; Bruno, M., Grosche, L. C. Desalin. Water 1963, 89, 31.
Treat. 2009, 2, 231. [CrossRef] [42] Allen, S. J.; McKay, G.; Khader, K.Y.H. Environ. Pollut.
[17] Cheriaf, M., Péra, J., Rocha, J. C. Cem. Concr. Res. 1999, 1989, 56, 39. [CrossRef]
29, 1387. [CrossRef] [43] Helby, W. A. Chem. Eng. 1952, 59, 153.
[18] Fungaro, D. A.; Silva, M. G. Quim. Nova 2002, 25, 1081. [44] Weber, W. J. Jr In: Weber W.J. Jr (ed) Physicochemical
[CrossRef] processes for water quality control, New York: Wiley-
[19] Fungaro, D. A.; Flues, M. S-M; Celebroni, A. P. Quim. Interscience, 1972.
Nova 2004, 27, 582. [CrossRef] [45] Zou, W.; Zhao, L.; Han, R. J. Radioanal. Nucl. Chem.
[20] Fungaro, D. A.; Izidoro, J. C.; Almeida, R. S.; Eclética 2011, 288, 239. [CrossRef]
Quim. 2005, 30, 31. [CrossRef] [46] Mall, I. D.; Srivastava, V. C.; Agarwal, N.; K.; Mishra, I.
[21] Fungaro, D. A.; Izidoro, J. C. Tchê Quím. 2006a, 3, 21. M. Chemosphere 2005, 61, 492. [CrossRef]

[22] Fungaro, D. A.; Izidoro, J. C. Quim. Nova 2006b, 29, 735. [47] Dubinin, M. M.; Radushkevich, L. V. Proc. Acad. Sci.
[CrossRef] USSR Phys. Chem. Sect. 1947, 55, 331.

[23] Querol, X.; Moreno, N.; Umaña, J. C.; Alastuey, A.; [47] Giles, C. H.; MacEwan, T. H.; Nakhwa, S. N.; Smith, D. J.
Hernández, E.; López-Soler A.; Plana, F. Int. J. Coal Geol. Chem. Soc. London 1960, 3973.
2002, 50, 413. [CrossRef] [48] Helfferich, F. Ion Exchange; McGraw-Hill: New York,
[24] Rayalu, S. S.; Bansiwal, A. K.; Meshram, S. U.; 1962.
Labhsetwar, N.; Devotta, S. Catal. Sur. Asia 2006, 10, 74. [49] Giles, C. H.; Smith, D.; Huitson, A. I. Theoretical. J.
[CrossRef] Colloid Interface Sci. 1974, 47, 755. [CrossRef]
[25] Carvalho, T. E. M.; Fungaro, D. A.; Magdalena, C. P.; [50] Giles, C. H.; MacEwan, T. H.; Nakhwa, S. N.; Smith, D. J.
Cunico, P. J. Radioanal. Nucl. Chem. 2011, 289, 617. Chem. Soc. London 1960, 3973.
[CrossRef]
[51] Mohd Din, A.T.; Hameed, B. H. J. Appl. Sci. in Environ.
[26] Izidoro, J. C.; Fungaro, D. A.; Santos, F. S.; Wang, S. Fuel Sanitation 2010, 5, 161.
Process Technol. 2012a, 97, 38. [CrossRef]
[52] Ho, Y. S., Carbon 2004,42, 2115. [CrossRef]
[27] Izidoro, J. C.; Fungaro, D. A.; Wang, S. Adv. Mater. Res.
2012b, 356-360, 1900. [CrossRef] [53] Ali, A. A.-H.; El-Bishtawi, R. J. Chem. Technol.
Biotechnol. 1997, 69, 27. [CrossRef]
[28] Fungaro, D. A.; Yamaura, M.; Carvalho, T. E. M. J. At.
Mol. Sci. 2011, 2, 305. [54] Çoruh, S.; Geyikçi, F.; Nuri O. N. ATINER'S Conference
Paper Series, Athens, Greece, 2012.
[29] Fungaro, D. A.; Graciano, J. E. A. Adsorpt. Sci. Technol.
2007, 10, 729. [CrossRef] [55] Gandhimathi, R.; Ramesh S.T.; Sindhu, V., Nidheesh P.V.
Iran J. Energy & Environ. 2012, 3, 52.
[30] Henmi, T. Soil Sci. Plant Nutr. 1987, 33, 517. [CrossRef]
[56] Eren E.; Cubuk, O.; Ciftci H.; Eren, B.; Caglar, B.
[31] Scott, J.; Guang, D.; Naeramitmarnsuk, K.; Thabuot, M. J. Desalin. 2010, 252, 88. [CrossRef]
Chem. Technol. Biotechnol. 2002, 77, 63. [CrossRef]
[57] Malarvizhi, R.; Ho, Y. S. Desalin. 2010, 264, 97.
[32] Shigemoto, N.; Hayashi, H.; Miyaura, K. J. Mater. Sci. [CrossRef]
1993, 28, 4781. [CrossRef]
[33] Kreuz, A. L. Utilização de cinzas pesadas de termelétricas
na substituição de cimento e areia na confecção de
concretos. [Master’s thesis.] Florianópolis, Brazil:
Departamento de Engenharia Civil da Universidade
Federal de Santa Catarina, 2002.

Orbital: Electron. J. Chem. 5 (3):179-191, 2013

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