Ion Exchange Technologies

375 Pages·13.78 MB·english

by  Kilislioglu A. (Ed.)

Chemistry » Electrochemistry
Ion Exchange Technologies

Edited by Ayben Kilislioglu,

ISBN 978-953-51-0836-8, 376 pages,

Publisher: InTech,

Chapters published November 07, 2012 under CC BY 3.0 license

DOI: 10.5772/2925

This book contains information about the technological development of ion exchange in their
application for industrial processes. Widely used and well known fields of ion exchange like
chromatography and electromembrane technology are described in this book with experimental
details. Designing new materials for nanotechnology and nanomaterials as ion exchanger are also
explained by experimental proofs. Ion exchange book is suitable not only for postgraduate
students but also for researchers in chemistry, biochemistry and chemical technology.

Editor: Prof. Ayben Kilislioglu
Istanbul University, Turkey
Professor Ayben Kilislioğlu is currently working in the
department of chemistry, Istanbul University (IU), Turkey.
She received her master of science degree in physical
chemistry from IU in 1994. She received her doctor of
philosophy degree in physical chemistry from IU in 2000.
She worked as visiting research assistant professor at the
University of Illinois, Chicago, department of chemistry,
between 2005-2006. She also worked at University of
Chicago in Dr. Graeme Bell’s Lab in 2007. She has research
experience in adsorption, surface characterization and ion
exchange. She worked on different projects funded by
Istanbul University Grant Commission. She has published
several research articles and a book chapter in this area.

EXPERIENCE
1994 - current
Istanbul University

EDUCATION
1981 – 1985
FMV Isik High school, Istanbul
1986 - 1995
Engineering, Istanbul University, Istanbul; Chemistry
1995 – 2000
Engineering , Istanbul University, Istanbul; Chemistry

EDITED BOOKS

Ion Exchange Technologies

PUBLICATIONS
Book ChapterThermodynamics of Ion
Exchange
by Ayben Kilisliogluin the book "Ion Exchange
Technologies" edited by Ayben Kilislioglu, ISBN 978-953-51-
0836-8, InTech, November 11, 2012
BOOK CONTENTS
Chapter 1 Thermodynamics of Ion Exchangeby Ayben Kilislioglu
Chapter 2 Ion-Exchange Reactions for Two-Dimensional
Quantum Antiferromagnetismby Yoshihiro Tsujimoto and Hiroshi Kageyama
Chapter 3 Bifunctional Polymer-Metal Nanocomposite Ion
Exchange Materials nech, Julio Bastos-Arrieta, Amanda Alonso
oz and Dmitri N. Muraviev
Chapter 4 Preparation of Ionic Polysilsesquioxanes with
Regular Structures and Their Ion-Exchange Behaviorsby Yoshiro Kaneko
Chapter 5 Carbon Nanomaterials – A New Form of Ion
Exchangersby Kriveshini Pillay
Chapter 6 Investigation of Sorption and Separation of
Lanthanides on the Ion Exchangers of Various Typesby Dorota Kołodynska and
Zbigniew Hubicki
Chapter 7 Ion Exchange in Glass – The Changes of Glass
Refractionby ski
Chapter 8 Selective Removal of Heavy Metal Ions from
Waters and Waste Waters Using Ion Exchange Methodsby Zbigniew Hubicki and
Dorota Kołodynska
Chapter 9 Ion Exchange and Application of Layered Silicateby
Kyeong-Won Park
Chapter 10 Structural and Ion-Exchange Properties of
Natural Zeoliteby Aiymgul M. Akimkhan
Chapter 11 Thermodynamic Study of the Synthesis of Zeolites
from Coal Ash and Its Use as Sorbents for Heavy Metals
rgio M. Soares and Vicente P. de Souza
Chapter 12 Influence of KNO3 Bath Composition on Ion
Exchange Process of Commercial Soda Lime Silicate Float Glassby Vincenzo M.
Sglavo
Chapter 13 Unheated and Heated Batch Methods in Ion
Exchange of Clinoptiloliteby Tevfik Unaldı and Selahattin Kadir
Chapter 14 The Role of Ion Exchange Chromatography in
Purification and Characterization of Moleculesby Hidayat Ullah Khan
Chapter 15 Nitrogen Isotope Separation by Ion Exchange
Chromatographyby Xingcheng Ding and Xunyue Liu
Chapter 1
Thermodynamics of Ion Exchange
Ayben Kilislioğlu
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/53558
1. Introduction
1.1. Ion exchange equilibria
During an ion exchange process, ions are essentially stepped from the solvent phase to the
solid surface. As the binding of an ion takes place at the solid surface, the rotational and
translational freedom of the solute are reduced. Therefore, the entropy change (ΔS) during
ion exchange is negative. For ion exchange to be convenient, Gibbs free energy change (ΔG)
must be negative, which in turn requires the enthalpy change to be negative because ΔG = ΔH
- TΔS. Both enthalpic (ΔHo) and entropic (ΔSo) changes help decide the overall selectivity of
the ion-exchange process [Marcus Y., SenGupta A. K. 2004]. Thermodynamics have great
efficiency on the impulsion of ion exchange. It also sets the equilibrium distribution of ions
between the solution and the solid. A discussion about the role of thermodynamics relevant to
both of these phenomena was done by researchers [Araujo R., 2004].
As the basic rule of ion exchange, one type of a free mobile ion of a solution become fixed on
the solid surface by releasing a different kind of an ion from the solid surface. It is a
reversible process which means that there is no permanent change on the solid surface by
the process. Ion exchange has many applications in different fields like enviromental,
medical, technological,.. etc. To evaluate the properties and efficiency of the ion exchange one
must determine the equilibrium conditions. At equilibrium conditions no mass diffusion and
concentration gradients occur through the surface of ion exchanger. Ion Exchange equilibria
can be explained by plotting the concentration(CsA+) or equivalent fraction(xsA) of A+ at the
surface versus the concentration (CA+) or equivalent fraction(xA ) of this ion in the equilibrium
solution. For monovalent ions the equivalent fractions are given by [1];
ms
xs  A
A msms
A B

© 2012 Kilislioglu, licensee InTech. This is an open access chapter distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
4 Ion Exchange Technologies
ms
xs  B (1)
B msms
A B
Where m denotes the concentration of the specified ions at the surface. Ion exchange
reactions may be described by the law of mass action using the activities of the ions, rather
than their concentrations [Bergaya et al., 2006];
asa
K B A (2)
asa
A B
where a and aare the activities of ions A+ or B+ in solution asand as the activities of
A B A B
these ions at the surface of the exchanger. K represents the thermodynamic equilibrium
constant. To explain ion exchange equilibria some common models are used. First type of
this model is based on the mass action law [Gorka et al., 2008; de Lucas et al., 1992; Melis et
al., 1995; Valverde et al., 1999]. In the second group ion exchange is treated as an adsorption
process [Gorka et al., 2008] and in the third, the solid phase is considered to provide sites
with fixed charges for ion exchange, as well as sites on which molecular adsorption takes
place[Gorka et al., 2008; Novosad & Myers,1982; Myers & Byington, 1986; Ioannidis &
Anderko, 2001].

Figure 1.
BASBSA
1.2. Ion exchange isotherm
The ion exchange equilibrium can be qualified by suitable equilibrium isotherms. These
isotherms are a graphical representation of the correlation between the equilibrium and
experimental terms at constant temperature. The concentration of an ion in the solid
expressed as a function of its concentration in the solution under specified conditions and at
constant temperature. The most common ion exchange isotherm represents solidarity
between ionic compositions of two phases: the ion exchange material and solution
[Zagorodni A. A., 2007]
Thermodynamics of Ion Exchange 5
The selectivity is a widely used characteristic of ion exchange systems. It shows the choice of
the material to one ion in comparison with another ion. The selectivity is a comparative
value. The easiest definition of selectivity can be done by comparing the equivalent fractions
of the ion in two phases. The exchanger is considered as selective towards one ion, if (at the
equilibrium state) the equivalent fraction of this ion in the exchanger phase is higher than in
the surrounding solution. Such a special selection characteristic usually depends on the
problem to be solved and on experimental data available [Zagorodni A. A., 2007].
In the presence of confounding processes (such as chemisorption, microbial degradation,
precipitation, and steric effects), selectivity coefficients can be used to generate exchange
isotherms utilizing a reverse order to the usual procedure [Bloom S. A. and Mansell R. S.,
2001].
Author details
Ayben Kilislioğlu
Department of Chemistry, Istanbul University, Turkey
2. References
Araujo R., (2004). Thermodynamics of ion exchange. Journal of Non-Crystalline Solids 349
(2004) 230–233 www.elsevier.com/locate/jnoncrysol.
Bergaya F., Lagaly G., and Vayer M. (2006). Cation and Anion Exchange, In: Handbook of Clay
Science, Elsevier Ltd.
Bloom S. A. and Mansell R. S. (2001) An algorithm for generating cation exchange isotherms
from binary selectivity coefficients SSSAJ Vol. 65 No. 5, p. 1426-1429
https://www.soils.org/publications/sssaj/articles/65/5/1426
De Lucas,A., Zarca,J., Canizzares, P.(1992). Ion-exchange equilibrium of Ca2+, Mg2+, K+and
H+ ions on amberlite IR-120:experimental determination and theoretical predictions of
the ternary and quaternary equilibrium data. Separation Science and Technology,
Vol.27,No.6, pp.823-841.
Gorka, A., Bochenek, R., Warchol, J., Kaczmarski, K., Antos D. (2008). Ion exchange kinetics
in removal of small ions. Effect of salt concentration on inter-and intraparticle diffusion.
Chemical Engineering Science, Vol.63,pp.637-650.
Ioannidis,S., Anderko, A. (2001). Equilibrium modeling of comoined ion-exchange and
molecular adsorption phenomena. Industrial and Engineering Chemistry Research, Vol.40,
No.2, pp. 714-720
Marcus Y., SenGupta A. K. (2004). Ion Exchange and Solvent Extraction A Series of
Advances Volume 16. ISBN: 0-8247-5489-1
Melis, S., Cao, G., Morbidelli, M. (1995). A new model fort he simulation of ion exchange
equilibria. Industrial and Engineering Chemistry Research, Vol.34, No.11, pp. 3916-3924.
6 Ion Exchange Technologies
Myers, A.L., Byington, S. (1986). Thermodynamics of ion exchange. Prediction of
multicomponent equilibria from binary data, In: Rodrigues,A.E.(Ed),Ion Exchange: Science
and Technology. NATO ASI Series E, No.107. Martinus Nijhoff, Dordrecht.
Novasad, J., Myers, A.L. (1982). Thermodynamics of ion exchange as an adsorption process.
The Canadian Journal of Chemical Engineering. Vol.60, No. 4, pp.500-503.
Valverde, J.L., De Lucas, A., Rodrigues, J.F.(1999). Comparison between heterogeneous and
homogeneous MASS action models in the prediction of ternary ion exchange equilibria.
Industrial and Engineering Chemistry Research. Vol.38, No.1, pp.251-259.
Zagorodni A. A., (2007). Physico-chemical Description of Ion Exchange Processes Ion
Exchange Materials, Pages 169-198
Chapter 2
Ion-Exchange Reactions for
Two-Dimensional Quantum Antiferromagnetism
Yoshihiro Tsujimoto and Hiroshi Kageyama
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/52111
1. Introduction
1.1. Insertion of metal halide array
Topotactic low-temperature reactions such as intercalation, deintercalation and ion-
exchange reactions provide a rational design of new structures of non-molecular extended
solids which are otherwise not accessible by conventional high-temperature solid-state
reactions [1-4]. Among candidate oxide materials used as a precursor of such reactions, the
most intensively studied system is the Dion-Jacobson (DJ) type layered perovskite (Figure
1). The chemical formula of the DJ phase is expressed as A´[An–1BnO3n+1], where A´ is an alkali
metal (Na, Rb, …), A is an alkaline earth or rare earth metal (Ca, Sr, La, …), B is a d0
transition metal (Ti, Nb, Ta, …), and n is the number of perovskite layers (2, 3, 4, …) [5, 6].
Here, alkali metal ions at the A´ site are highly reactive because of ionic (i.e., weak) A´-O
bonding, while the perovskite unit [An–1BnO3n+1] is strongly bonded and is chemically inert.
By exploiting ion-exchange reactions with various reagents, a wide variety of new or
improved chemical and physical functionalities including (photo)catalysis [7, 8], ionic
conductivity [9] and superconductivity [10] have been developed. However, ion-exchange
reactions are rarely employed for the purpose of materials design toward low-dimensional
magnetism, because those who work in this filed (mostly physicists) are not familiar with
such chemical processing. In addition, compounds obtained by soft-chemical approaches
involve negative effects on the crystal structure, for example, poor crystallinity, non-
stoichiometry and defects. In particular, it is known that a tiny defect can easily destroy or
mask intrinsic magnetic properties of low-dimensional quantum systems.
In 1999, John B. Wiley et al. in the University of New Orleans reported a new type of ion-
exchange reactions involving the simultaneous co-exchange of transition-metal cation and
chloride anion [11]. As shown in Figure 1(a) and 1(b), the reactions of the n = 2 and 3 DJ

© 2012 Tsujimoto and Kageyama, licensee InTech. This is an open access chapter distributed under the
terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.