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Article history:
Received 1 December 2013
Received in revised form 2 May 2014
Accepted 9 June 2014
Available online 19 June 2014
Keywords:
Natural zeolite
Surfactant modication
Anions sorption
FT-IR spectra
a b s t r a c t
This work presents results of FT-IR spectroscopic studies of anionschromate, phosphate and
arsenate sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption
has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite,
ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA+) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of
organo-zeolites were measured. Their values are 17 mmol/100 g for chabazite, 4 mmol/100 g for mordenite and ferrierite and 10 mmol/100 g for clinoptilolite. The used initial inputs of HDTMA correspond to
100% and 200% ECEC of the minerals. Organo-modicated sorbents were subsequently used for immobilization of mentioned anions.
It was proven that aforementioned anions sorption causes changes in IR spectra of the HDTMAzeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations
are due to bands corresponding to the characteristic SiO(Si,Al) vibrations (occurring in alumino- and
silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations
have also been observed. Systematic changes in the spectra connected with the anion concentration in
the initial solution have been revealed.
3
3
The amounts of sorbed CrO2
4 , AsO4 and PO4 ions were calculated from the difference between their
concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption
experiments. Concentrations of anions were determined by spectrophotometric method.
2014 Elsevier B.V. All rights reserved.
Introduction
Natural zeolites are a group of crystalline, hydrated tectoaluminosilicates characterized by varied and extremely valuable physicochemical properties. One of the most signicant is the ability
of sorption and separation of ions and molecules. Due to the high
K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882
877
Experimental
Studies presented in this work were divided into several stages:
(1) transformation zeolites into sodium form; (2) modication of
them with HDTMA-Br; (3) sorption of selected anions using
obtained sorbents; and (4) MIR spectroscopic studies of organozeolites after anions sorption.
In order to improve the ion exchange properties, all zeolites
were transformed into sodium forms. The Na-forms of sorbents
were exchanged with hexadecyltrimethylammonium cations
(HDTMA+) [8,10] in amount equivalent to 100% (1.0) and 200%
(2.0) ECEC of each of the zeolites. The value of ECEC in relation to
HDTMA+, determined by sorption of alkylammonium ions, are
17 mmol/100 g, 4 mmol/100 g, 4 mmol/100 g and 10 mmol/100 g
respectively for chabazite, mordenite, ferrierite and clinoptilolite.
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Fig. 2. Sorption isotherm of: (a) chromate, (b) phosphate and (c) arsenate ions on chabazite, mordenite, ferrierite and clinoptilolite after HDTMA-modication.
K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882
879
Fig. 2 (continued)
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K. Barczyk et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 133 (2014) 876882
Fig. 4. MIR spectra of: (a) clinoptilolite and (b) mordenite modied with 2.0 ECEC of
HDTMA before and after sorption of different ions form the aqueous solution with
5 mmol/dm3 initial concentration in the range of 30402800 cm 1.
Fig. 3. MIR spectra of: (a) chabazite and (b) clinoptilolite modied with 2.0 ECEC of
HDTMA before and after sorption of different ions form the aqueous solution with
5 mmol/dm3 initial concentration.
The most effectively sorbed anions are chromates, which sorption capacities on zeolites modied with 2.0 of ECEC are 198, 112,
77 and 56 mmol/kg, respectively for chabazite, clinoptilolite, ferrierite and mordenite. In contrast, sorbents modied with HDTMA
in amount equivalent to 1.0 the ECEC removed little more than a
half of maximum amount sorbed anions on zeolites modied with
double layer of HDTMA. Trivalent anions, like phosphates and arsenates, are removed to a much lesser extent, and their anion
exchange capacities do not exceed 50 mmol/kg for AsO34 and
35 mmol/kg for PO34 .
These results clearly show that differences in sorption capacity
are caused by many factors, like the type of anion, its charge and
speciation in aqueous solution. The removal of oxyanions from
aqueous solution depends strongly on the pH of the solution,
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881
Fig. 5. MIR spectra of chabazite modied with 2.0 ECEC of HDTMA before and after
sorption of different ions form the aqueous solution with 5 mmol/dm3 initial
concentration in the range of 840680 cm 1.
the biggest shift is visible for these anions (about 4 cm 1), whilst
the smallest shift refers to AsO34 and PO34 ions, which are sorbed
to a much lesser extent.
In the fourth analyzed region (860680 cm 1) bands which concern two types of vibrations realized in zeolites structure occur
(g. 5). The rst type related to bands at ca. 776 cm 1 and
635 cm 1 originates from pseudolattice vibrations of aluminosilicate structure of zeolites. The anion sorption process is limited
only to external surface of organo-zeolites, hence the bands connected with the internal SiO(Si) and SiO(Al) vibrations in tetrahedra or alumino- and silico-oxygen bridges remain unchanged.
The second group of bands is connected with HDTMA+ modication. The bands at ca. 730 and 720 cm 1 correspond to the
CH2-rocking mode [22]. The bands responsible for these vibrations
are splitted, which is a consequence of intermolecular interaction
between the two adjacent hydrocarbon chains in perpendicular
orthorhombic cell [21,22]. As can be noticed, the rocking vibrations
in methylene group are preserved at essentially unchanged frequencies during anions sorption process. At the same time, the
integral intensity of these bands decreases with the increase of
concentration in the initial solution. As in the case of the bands
in the second analyzed region, the most visible changes are
observed for chromates, because CrO24 ions are sorbed the most
effectively form all anions.
Conclusions
Based on obtained results the following conclusions can be
drawn:
Organic modication with the use of HDTMA+ leads to change
of the surface properties of all analyzed zeolites, giving them
the ability to anions sorption.
The anion sorption capacity of SMZ depends on the kind of
anion and its initial concentration in the solution, as well as
on the type of zeolite and its surfactant loading level.
Sorbents modied with 2.0 of ECEC of each of zeolites show
greater anion sorption than materials modied with 1.0 of
ECEC, and have a bigger afnity for chromates than for
arsenates and phosphates.
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Acknowledgments
Financial support this work was provided by AGH University of
Science and Technology in Krakow under Grant No. 15.11.160.114.
The authors would like to thank Dr. T. Bajda from Faculty of
Geology, Geophysics and Environmental Protection AGH University of Science and Technology for his help during measurements
of anion sorption capacity of SMZ.
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