Journal of Colloid and Interface Science 281 (2005) 6879

www.elsevier.com/locate/jcis

The concept of capacity in zeolite ion-exchange systems

Vassilis J. Inglezakis
National Technical University of Athens, School of Chemical Engineering, General Chemistry Lab.,
Heroon Polytechniou 9 Str., Zografou, 157 73 Athens, Greece
Received 10 June 2004; accepted 10 August 2004
Available online 5 October 2004

Abstract
In the present paper a study is conducted in order to distinguish the several types of capacity used in the literature on zeolite ion-exchange
systems, to verify the use of each capacity type, and to analyze the several experimental methods used for capacity determination. Although
the study is focused on zeolite clinoptilolite as a characteristic paradigm, its theoretical approaches and experimental findings and methods
could also apply to other zeolites.
2004 Elsevier Inc. All rights reserved.

Keywords: Zeolites; Capacity; Ion exchange; Clinoptilolite

1. Introduction changers such as zeolites are studied. These phenomena and

Zeolites are widely used in ion-exchange applications,
where they exchange cations from their structure with dis-
solved ones. Ion exchange is one of the methods used for the
removal of several toxic substances, including heavy metals,
from industrial and municipal wastewater [1,2]. Clinoptilo-
lite is one of the zeolite species and is found in abundance
in many deposits around the world. It belongs to the heulan-
dite group, with a three-dimensional framework of silicon
and aluminum tetrahedra, having the typical chemical for-
mula Na6 [(Al2 O3 )(SiO2 )30 ]24H2O [3]. The most important
property of zeolites is the ion-exchange capacity expressing
the ability of the material to take up cations.
Proper experimentation and unified terminology are im-
portant tasks in any field of science. To obtain reliable and
comparable results requires careful consideration of many
experimental factors. For example, as will be discussed
later, ion-exchange experiments performed using fixed-bed
columns may result in erroneous results, since columns may
suffer from flow nonidealities. Many other interfering phe-
nomena may be present, especially when inorganic ion ex-
* Fax: +30-2107723285.
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0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.082
differences in experimental procedures, as well as differ-
ences in terms used to define a measured quantity, are a
major cause for poor comparability of ion-exchange data ob-
tained by different authors for a given system.
More specifically, considerable confusion can arise from
the fact that in the field of zeolite science various concepts
of zeolite capacity are encountered and various kinds of ca-
pacities, measured by different experimental methods, are
used. Ion-exchange capacity is often determined simply by
equilibrating batchwise a sample of an ion exchanger with a
solution of an ion and calculating the capacity from the up-
take value thus obtained. As will be analyzed, this is by no
means an appropriate method to determine the capacity: it
only gives the amount of the specific ions taken up by a unit
amount of the ion exchanger in the specific conditions used
in the experiment.
On the other hand, it is well known that capacity is needed
in several determinations, such as the normalization of equi-
librium isotherms and the application of kinetic models in
order to determine ion-exchange diffusion coefficients. The
differences in the exchange isotherms derived by different
researchers for the same ion-exchange systems are mainly
due to the assumption of different cation-exchange capaci-
ties for the zeolitic material [4,5].
 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
The aim of the present study is to review the already
known theoretical considerations and experimental methods
for the subject of capacity, to clarify the meaning and the use
of zeolite capacity, and to propose a unified capacity termi-
nology.
2. Ion exchange and capacity
2.1. Capacity definitions
IUPAC recommendations on ion-exchange nomenclature
define the following capacity types [6,7]:
Theoretical (specific) capacity is the number of iono-
genic groups per specified amount of ion exchanger.
This type of capacity is a constant used for character-
izing ion exchangers. For the same capacity type, Helf-
ferich used the term capacity (maximum capacity, ion-
exchange capacity) [1].
Helfferich used the term apparent capacity (effective
capacity) [1]. According to Helfferichs definition, ap-
parent capacity is the number of exchangeable counter
ions per specified amount of the material and depends
on the experimental conditions.
Practical (specific) capacity is the total amount of
ions taken up per gram of ion exchanger under spe-
cific conditions, which should be always given. Practical
capacity may be lower than the theoretical exchange ca-
pacity if the experimental conditions do not allow full
exchange [6].
Useful capacity (defined by Helfferich) [1] is the capac-
ity utilized when equilibrium is not attained. Depends
on experimental conditions.
Breakthrough capacity (IUPAC and Helfferich) is the
capacity utilized in column operations. Depends on the
experimental conditions.
2.2. Ion exchange
In order to clarify the above definitions some basic the-
oretical concepts will be analyzed. As is well known, ion
exchange is the exchange of ions between a liquid and a
solid phase. The solid phase is charged and this charge is
balanced by ions of the opposite charge, named counterions.
When the ion exchanger, containing ions A, is immersed in
a liquid phase, containing ions B, then a diffusion process is
established where A ions diffuse out from and ions B diffuse
into the solid structure. This diffusion is a result of the con-
siderable concentration difference between the phases [1]. If
the ions carried no electric charges, these concentration dif-
ferences would be leveled out by diffusion. However, such
a process would disturb electroneutrality since, actually, the
ions are charged. Eventually, an equilibrium is established in
which the tendency of the ions to level out the existing con-
centration differences is balanced by the action of the solids
69
electric field [1]. Thus, the most important property of the
solid phase is its active charge, which is straightforwardly
related to its ion-exchange capacity.
In the definition of theoretical capacity the term iono-
genic groups is included. Ionogenic groups can be defined
easily in the case of resins. Resins are typical gels. Their
framework, the so-called matrix, consists of an irregular,
macromolecular, three-dimensional network of hydrocar-
bon chains. The matrix carries ionic groups such as SO 3,
COO , and PO2 3 . These radicals are fixed in the frame-
work and are the ionogenic groups of the resins. However,
these ionogenic groups are not always ionized. For example,
a typical weak acid group is the fixed radical COO . This
is a fixed ionogenic group ionized only at high pH. At low
pH, the fixed radical is combined with H+ , forming undisso-
ciated COOH, and thus no longer acts as a fixed charge [1].
In other words, it is inactive in respect to ion exchange. This
is why Helfferich states that only when they are ionized
do the ionogenic groups act as fixed charges which must be
balanced by counter ions [1]. For that reason, Helfferich
introduced the term available capacity in order to cover
the part of the theoretical capacity which is actually avail-
able. Strong-acid and strong-base groups are, by definition,
practically completely ionized under any conditions [1]. The
apparent capacity of resins with such groups thus is essen-
tially constant and equivalent to the theoretical capacity.
In zeolites there are no separate ionogenic groups: in fact
there is a lack of definite ionogenic groups [6]. In the case
of zeolites, the lattice consists of SiO4 and AlO4 tetrahedra,
which have their oxygen atoms in common. Since aluminum
is trivalent, the lattice caries a negative electric charge. This
charge is balanced by alkali and alkaline earth cations which
do not occupy fixed positions, but are free to move in the
channels of the lattice framework; these ions act as coun-
terions and can be replaced by other cations [1]. Thus, the
negative charge of zeolites is not localized but is more or less
uniformly distributed in the framework [6]. Furthermore, un-
like the charge in resins, the framework charge does not
depend on external conditions. In the case of zeolites the
term ionogenic groups, which are essentially fixed radi-
cals, is more conveniently replaced by the term framework
charge. In zeolites the framework charge is balanced by free
cations and in that case these cations are the counterions in
Helfferichs terminology. In the case of resins, the ionogenic
groups may be partially inactive. Then counterions are those
cations that associate to the active ionogenic groups (fixed
charges).
Another difficult term is exchangeable cations or
exchangeable counterions. By exchangeable, Helfferich
meant the part of resin cations that are free to move and
participate in ion exchange. Essentially, these cations are the
counterions balancing the charge of the ionized ionogenic
groups (fixed ionic groups). Similarly, in zeolites, exchange-
able cations are the cations that are balancing the framework
charge. In both cases, the part of the exchangeable cations
that will eventually be exchanged is dependent on the experi-
70 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
mental conditions. However, in resins the active fixed charge
of the solid phase depends on the experimental conditions:
in zeolites the framework charge is constant.
In conclusion, it can be stated that during the diffusion
process, the framework charge of zeolites is forming a non-
localized electric field which is influencing the exchange
process regardless of a complete or partial exchange of its
balancing cations. However, the active charge in resins may
be different from case to case and the exchangeable cations
are at the same time equal to the ionized ionogenic groups.
Although the IUPAC and Helfferich definitions may
cover many ion-exchange systems (mainly resins), the spe-
cific nature of natural zeolites creates a need for the intro-
duction of new capacity type definitions. In the following
paragraphs the several types of capacities will be separated
into three groups. In these groups seven types of capaci-
ties will be included: ideal exchange capacity, theoretical
exchange capacity, real exchange capacity, maximum ex-
change level, operating capacity, breakthrough capacity, and
effective capacity.
3. Proposed terminology
3.1. Ideal, theoretical, and real exchange capacity
3.1.1. Definitions
In the present paper, in the IUPAC definition of theoret-
ical exchange capacity (TEC) the term exchangeable cat-
ions instead of ionogenic groups will be used. The total
charge of these exchangeable cations is equal to the zeolite
framework charge. A common method for the determina-
tion of the theoretical exchange capacity of ion exchangers
(including zeolites) is chemical analysis of the material [1,
812].
It is well known that zeolites are rarely found in nature in
their pure form. Considering zeolite tuffs, containing sev-
eral impurities which can be active or inactive in respect
to ion exchange, TEC is expressing the amount of possible
exchangeable cations. However, in the case of pure zeo-
lites, TEC corresponds to the actual amount of exchangeable
cations. In order to distinguish the case of pure zeolites TEC
the term ideal exchange capacity (IEC) is introduced.
Real exchange capacity (REC) refers to the amount of the
actual exchangeable cations of the zeolite, measured by ion-
exchange methods, and is a characteristic constant of the ion
exchanger independent of the experimental conditions. The
total charge of the exchangeable (removable) cations is equal
to the active negative charge of the zeolite structure [8]. Es-
sentially, REC is the upper limit of actual zeolite capacity.
In the case of zeolite ores (tuffs), TEC is always higher
than REC; this difference is due to the fact that some of the
zeolite cations cannot be removed from the zeolite structure
because of strong bonding forces within the structure of the
material, or they are part of the material impurities and thus
they are not exchangeable [1,4,13,14]. Obviously, REC is
equal to IEC in the case of pure zeolites.
In conclusion, IEC is a characteristic property of pure
zeolite species, while TEC and REC are characteristic prop-
erties of a zeolite sample (tuff ) with a specific purity. The
values of TEC and REC depend on the amount and the na-
ture of impurities.
3.1.2. Minerals found in zeolite ores: the case of
impurities
In this section the minerals that frequently coexist with
zeolites in ores will be analyzed. This analysis is important,
because these minerals (or other impurities) could be active
(or inactive) with respect to ion exchange and thus they could
influence the exchange capacity of the zeolite tuff.
Clinoptilolite is found along with other minerals of sil-
icate class: feldspars, quartz and other zeolites (members
of the tectosilicates subclass), clays (members of the phyl-
losilicates subclass), and volcanic glass [4]. From the zeolite
group clinoptilolite can be found along with heulandite and
mordenite, which are materials of high cation capacity.
Feldspars are anhydrous aluminosilicates of potassium,
sodium, and calcium. The silicons and aluminums occupy
the centers of interlinked tetrahedra of SiO4 and AlO4 .
These tetrahedra connect at each corner to other tetrahedra,
forming an intricate, three-dimensional, negatively charged
framework. The potassium, sodium, and calcium sit within
the voids in this structure. Thus, feldspars can exchange
these cations with others.
Most clays are chemically and structurally analogous to
other phyllosilicates but contain varying amounts of water
and allow more substitution of their cations. These cations
are exchangeable [15]. The most important clay minerals
related to zeolite ores are kaolinite (Al2 Si2 O5 (OH)4 ), smec-
tites (vermiculite and montmorillonite(Ca, Na, H)(Al,
Mg, Fe, Zn)2(Si, Al)4 O10 (OH)2 xH2 O)), and illite ((K, H)
Al2 (Si, Al)4 O10 (OH)2 xH2 O). It is well known that clays
exhibit high cation exchange capacities [16]. Several studies
have been published on ion exchange of Cs+ , U, NH+ 4,K ,
+
Na+ , Ca2+ , and Mg2+ on several clays such as montmo-
rillonite, vermiculite, and illite [15,17,18]. The cation-ex-
change capacity of smectites is 80150 meq/100 g, of illites
1040 meq/100 g, and of kaolinites 315 meq/100 g [19].
From the quartz group, clinoptilolite is found along with
quartz and cristobalite [16]. Quartz is a neutrally charged
inert mineral. Quartz has a three-dimensional rigid frame-
work but does not have the capacity for cation exchange,
as there are no aluminum atoms present. Aluminum is im-
portant because it is replacing part of the silicon atoms in
the framework of silicates (aluminosilicates) and creates a
charge imbalance (negatively charged structure). It is char-
acteristic that sandy soils, which contain large amounts of
quartz, have cation-exchange capacities lower than 23.5
meq/100 g [19].
 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
Finally, several inorganic compounds are present, such
as the calcium and magnesium carbonates calcite (Ca),
dolomite (Ca, Mg), and magnesite (Mg) [2023].
3.2. Maximum exchange level and operating capacity
In the IUPAC definition, it is not clear if the practical
specific capacity is the capacity utilized under equilibrium
conditions. On the other hand, available capacity in Helf-
ferichs terminology refers to equilibrium conditions; for
capacity measurements under nonequilibrium conditions,
Helfferich uses the term useful capacity.
In any case, even if practical (and available) capacity is
referring to the loading achieved under equilibrium condi-
tions, it is not clear which is this equilibrium loading. For a
specified ion-exchange system, practical capacity could be
equal to one of several equilibrium points of its equilibrium
curve. The point which corresponds to the saturation of the
Fig. 1. Typical equilibrium curve.
Fig. 2. Relationship between IUPAC (and Helfferichs) definitions and the definitions introduced in the present paper.
71
ion exchanger (upper limit of equilibrium loading), with a
specific ion under specified normality and temperature, is
more important than the other equilibrium points (see Figs. 1
and 2). In the present paper, a specific term is used for that
saturation equilibrium loading: this term is maximum ex-
change level. This type of capacity is equivalent in nature
to the apparent capacity of resins in Helfferichs terminol-
ogy.
Maximum exchange level (MEL) is a characteristic prop-
erty of the specific ion-exchange system. An ion-exchange
system is defined here as a system consisting of a mater-
ial and a liquid solution which contains the ion to be ex-
changed, under a specified temperature and normality. MEL
is straightforwardly related to the equilibrium behavior of
the specific ion-exchange system and like the equilibrium
isotherm depends only on the temperature and the normality
of the solution.
The maximum exchange level (MEL) is measured by re-
peated equilibrations or by determinations using equilibrium
data (equilibrium isotherm) and is expressed in terms of
exchangeable ions per unit mass of the exchange material
[20,24]. This type of capacity is frequently used in zeolite
science and is well defined [9,20,24].
Furthermore, MEL can be measured using column exper-
iments [1]. However, in practice, under dynamic conditions,
such as in the case of column experiments, the achieved
capacity is influenced by the operational conditions: liquid
flow rate (or contact time) and flow quality [20,25,26]. Thus
this kind of capacity is frequently found to be different in
value, with respect to MEL, and it is well known as oper-
ation capacity (OC) [1]. OC is equal to MEL in the case of
infinite contact time and ideal flow in column operation [26].
Practically, MEL is always higher than OC.
MEL and REC could be equal for ideal ion-exchange
systems, i.e., systems where complete exchange is achieved.
This is the case for most of the meso- and macro-porous ion-
72 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
exchange materials such as resins. For example, in Lewatit
resin (a sulfonated polystyrene resin), the saturation capac-
ity (MEL according to our terminology) for Ni2+ , Cu2+ , and
Mn2+ is essentially the same in a wide range of solution nor-
mality (0.011 eq/L) [27]. This is why the authors state that
exchanger saturation capacity is a parameter usually con-
sidered as a characteristic constant and independent from
the involved cations [27].
However, generally, MEL is only a fraction of REC and
this is the case of partial exchange. Partial exchange in zeo-
lites is mainly a result of the ion-sieving phenomenon in the
microporous structure and thus the nature (shape, size, and
charge) of the incoming cation is critical [1]. Also, this dif-
ference in capacity is due to the fact that some of the zeolite
cations cannot be removed easily or even at all under the spe-
cific experimental conditions, because of low mobility and
strong bonding forces within the structure of the material [1,
13,14]. Thus, MEL also depends on the characteristics of the
outgoing (zeolite) cations. This is why, frequently, the zeo-
lites are pretreated and converted to the so-called homoionic
forms, mainly in Na-form: for example, it is well known that
Na+ ions are the weakest bound ions in clinoptilolite and
thus they are most easily exchanged with cations from solu-
tions [2830]. Finally, temperature is a critical factor, as it
influences the equilibrium and kinetics of the ion-exchange
system [1]. For example, in clinoptilolite systems the level
of exchange of zeolite Ca2+ ions by 1 M Cs+ and Na+ so-
lutions was found to be 59% and 57% at 5 C and 91% and
100% at 90 C, respectively [31]. In those cases, MEL is in-
creased, but in every case, REC is active and independent of
the conditions.
3.3. Effective and breakthrough capacity
According to Helfferichs and IUPAC definitions, break-
through capacity is the loading of the ion-exchange mater-
ial in a column (fixed bed) when the incoming ion is first
detected in the effluent or when the concentration in the ef-
fluent reaches some arbitrarily defined value [1,6]. Since the
level at which the ion is first detected in the effluent mainly
depends on the sensitivity of the analytical method used to
measure the breakthrough, this part of the breakthrough ca-
pacity definition is rather diffuse. Instead, the use of a spe-
cific concentration in the effluent for the determination of
that capacity is more clear. This kind of capacity completely
depends on the arbitrary selection of breakpoint concentra-
tion: in practical use of ion exchangers it is appropriate to
use certain breakthrough levels such as 110% [6].
As pointed out previously, the term maximum exchange
level is introduced for the upper limit (saturation) equilib-
rium loading. The other equilibrium loadings (included in
the term practical specific capacity), as well as the use-
ful capacity (nonequilibrium loading), can be grouped in one
term expressing the available capacity under specified exper-
imental conditions. Typically, a kinetic experiment results in
several loadings for several time intervals and a final equi-
Fig. 3. Typical kinetic curve.
librium loading which is in turn a point on the equilibrium
curve. Thus, several kinetic experiments eventually result
in a corresponding number of equilibrium points. All equi-
librium and nonequilibrium loadings, except the saturation
equilibrium point, can be grouped under the term effective
capacity. In Figs. 1 and 3 the several experimental points
are presented.
Effective capacity (EC) can be defined as the amount of
the cations of the zeolite contained in a specific amount of
the material, which are exchangeable under specific exper-
imental conditions. In the present paper this term is used
only for batch-type effective capacity, as the breakthrough
capacity covers the case of column-type effective capacity.
EC could be equal to MEL if an infinite contact time and
ratio of solution volume to solid mass is used.
Concluding, effective (EC) and breakthrough capacities
(BC) depend not only on the specific ion-exchange system
but also on the experimental conditions used for its determi-
nation.
Experimental conditions are the liquid-volume-to-solid-
mass ratio, agitation rate, and contact time for batch systems
and the volumetric flow rate and breakpoint concentration
for column systems (temperature and normality of the solu-
tion are characteristic properties included in the term ion-
exchange system).
In Fig. 2 the relationship between Helfferichs (and the
IUPAC) definitions and the definitions introduced in the
present paper is diagrammatically presented.
Finally, from the analysis it is clear that TEC
REC

MEL
OC
EC, BC.
4. Experimental methods for capacity measurements
4.1. Theoretical exchange capacity
In the case of a zeolite tuff, TEC is determined after
chemical analysis of the material. The exchangeable cations
of zeolites are Mg, Ca, K, and Na. Thus TEC is the total sum
 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
Table 1
Ideal exchange capacity of some natural zeolites: data calculated using the
unit cell formula
Zeolite Cation exchange capacity
(meq/g)
Chabazite 3.84
Clinoptilolite 2.16
Erionite 3.12
Ferrierite 2.33
Heulandite 2.91
Laumontite 4.25
Mordenite 2.29
Phillipsite 3.31
Faujasite 3.39
of the zeolite (free) cations [3,32]:

rium isotherms [10,3840], a method which is, however,
TEC = (Na, K, Mg, Ca). (1)
In the case of a pure zeolite, its chemical formula can be
used for the determination of IEC. Then the amount in equiv-
alents of the exchangeable cations for each formula unit can
easily be calculated. The weight of a formula unit is cal-
culated by adding up the atomic weights of the constituent
atoms and finally the capacity is expressed as meq/g.
In Table 1 the IEC for several zeolites is presented, based
on the chemical formula of pure species [33].
Ideal exchange capacity, estimated for 100% clinoptilo-
lite-rich rocks (20 samples) from chemical formulae, is re-
ported to be 2.32 0.12 [5].
4.2. Effective capacity
Effective capacity (EC) of the samples can be measured
under several arbitrarily chosen conditions: thus there are
no specific experimental conditions for this measurement.
EC depends on the experimentalist to choose the appropriate
conditions in order to have representative results. Effective
capacity can be measured easily in batch systems and for a
specific ion-exchange system it depends on the solid-mass-
to-liquid-volume ratio, agitation rate, and contact time. The
solution-volume-to-exchanger-mass ratio used in effective
capacity measurements has certain practical limits. When
usual laboratory equipment is used, this ratio cannot be very
low or high in order to have enough solution or exchanger
available for analysis. Ratios between 10 and 100 ml/g are
commonly used, 1000 ml/g often being a practical upper
limit [6].
4.3. Maximum exchange level
Maximum exchange level of ion-exchange materials
is commonly measured using the repeated equilibrations
method [1]. MEL studies are conducted as follows: A mea-
sured quantity of zeolite is added to a vessel containing a
measured volume of a cation solution of known initial con-
centration. The solution is analyzed periodically with time
for cation concentrations and then it is replaced with a fresh
73
solution of the same cation until no further uptake from
zeolite is observed [20]. Exchange temperature is kept con-
stant during the batch reaction time. A repeated equilibration
procedure, using several concentrations or renewals of satu-
ration solutions, is used for several forms of clinoptilolites,
zeolites and other tuffs, active carbon, bones, and ceramics
in order to evaluate the maximum exchange level (also called
specific-cation exchange capacity) of NH+
2+ 2+
4 , Cu , Zn ,
2+ + + 2+
Cd , Li , Cs , and Pb [5,24,3436]. A similar proce-
dure, referred to as exhaustive equilibration, was applied
in Y zeolites, clinoptilolite, ferrierite, and mordenite for the
determination of maximum exchange levels of Cu2+ , NH+ 4,
and Pb2+ [9,22,37].
An alternative to the repeated equilibration method is the
estimation of maximum exchange levels using the equilib-
time-consuming, since it needs the experimental points from
the whole range of the equilibrium curve and is suspect
of errors resulting from the fit of the equilibrium equation
to experimental data [38]. The Langmuir isotherm is fre-
quently used for ion exchange on clinoptilolite, e.g., for ion
exchange of NH+ 2+ 2+
4 , Cd , Pb , and other cations [26,41
44].
The Langmuir equation in its linear form is used to cor-
relate the equilibrium data,
qmax bC C 1 1
q= = C+ , (2)
1 + bC q qmax bqmax
where q is particle-phase equilibrium concentration in mg/g,
C is liquid equilibrium concentration in mg/L, qmax is ulti-
mate capacity of the material in mg/g, equivalent to MEL in
our terminology, and b is the Langmuir equilibrium constant
(L/mg). Then the slope and the intercept of the line are used
for the determination of the isotherm constants.
4.4. Real exchange capacity
4.4.1. XRD method
In the case of a zeolite tuff of known composition, REC
can be calculated using the following equation


REC = Pi IECi , (3)
i
where Pi is the fraction of each mineral (zeolite or impu-
rity) i in the zeolite tuff having an ideal exchange capacity
of IECi . The limitation of this equation is that the process to
identify and quantify the minerals that are part of a zeolite
tuff is difficult and time-consuming and even in that case the
IEC of each mineral should be known.
It has been suggested that there should be a linear corre-
lation between zeolite content and real exchange capacity
of the bulk sample for ideal cases [45,46]. The basic as-
sumption is that several minerals or impurities, contained in
the zeolite tuff, are inactive regarding ion exchange (such as
quartz, for example). Thus, Eq. (3) is simplified to
REC = pIEC, (4)
74 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
where p is the fraction of the zeolite in the tuff (purity),
having an ideal exchange capacity of IEC. This equation is
linear and the results can be easily presented graphically.
While IEC are readily available in the related literature
(Table 1), the mineral content of a tuff should be experimen-
tally evaluated. Among the traditional methods for quanti-
tative phase analysis of natural mineral samples, X-ray dif-
fraction techniques (XRD) are widely used [47,48]. They are
based on the fact that the intensities of specific diffraction
peaks from a given phase are related to the phase abundance
in a mixture. These methods use integrated intensities of se-
lected reflections and need calibration curves using internal
or external standards. Several XRD-based methods are avail-
able for quantitative analysis of minerals. The most effective
is the Rietveld method, which requires a structural model for
each major mineral present in the mixture and is therefore
limited to minerals having well-defined structures [49,50].
Another method is to use pure mineral species as intensity
references [49,51].
Several limitations of XRD methods exist, as discussed
in the related literature [48]. Many crystalline substances
are strong diffractors of X-rays and can be detected when
present in concentrations as small as 12%. Other materials
diffract X-rays less efficiently and yield diffraction patterns
of measurable intensity only when they constitute a major
portion of the sample. As a result, certain minor constituents
cannot be identified by XRD alone. Furthermore, it is known
that X-ray line intensities may not always be proportional to
the zeolite contents [51]. For these reasons, XRD methods
should be used along with other methods for the determina-
tion of zeolite capacity.
4.4.2. Ion-exchange methods
Real exchange capacity is representing the (negative)
framework charge of the zeolite structure; thus, the goal of
a REC determination method is to estimate all the cations
of the zeolite that could be exchanged from the solid phase.
This means that the zeolite cations should be exhaustively
(totally, fully) exchanged: in other words, the zeolite nega-
tive charge should be balanced by an equivalent amount of
incoming cations. This total (exhaustive) exchange could be
achieved by
(a) repeated equilibrations in batch systems with periodical
renewal of the solution phase [5,5154];
(b) one simple equilibration in a batch system using a high
solution-volume/zeolite-mass ratio [32,55];
(c) under dynamic conditions (in columns): the term cross-
exchange method is used in order to present this proce-
dure [5].
These exchanges are essentially a procedure of satura-
tion of the zeolite with an incoming cation from a solu-
tion and the result is to convert the zeolite to its homoionic
form. Conversion of all exchangeable ions to one species
(homoionic form) is a common step for cation-exchange ca-
pacity determinations [21,44,51,5659]. According to Sirke-
cioglu and Erdem-Senatalar, zeolites should be converted to
near-homoionic form in order to eliminate as much as pos-
sible the well-known effects of the variation of the cationic
composition with location on capacity [51]. During the ho-
moionic form preparation there are two different ways to
determine the REC: by chemical analysis of the solid or liq-
uid phase.
Obviously, great care should be taken to ensure the attain-
ment of full conversion to the desired homoionic form. In
both cases, whether done in columns or batchwise, the max-
imum uptake may not represent the real exchange capacity
of the material. This is the case, for example, when various
ions have different accessibilities to the exchange sites [6].
The most favorable conditions for successful cation loading
of ion-exchange materials should be the use of cations of
low valence and large ionic radius (small hydrated radius)
using increased temperature and rather high pH [60]. By
increasing the temperature at which exchange is performed
the attainment of full exchange of the zeolite cations is en-
abled. For example, it is well known that overall exchange
of cations out of the clinoptilolite is favored at higher tem-
peratures [23,31]. However, this is not always the case, as
for example in Na-homoionic synthetic Y zeolites, since it
is found that the maximum exchange levels of Cu2+ are not
significantly influenced by temperature in the range of 25
100 C (differences lower than 8%) [37]. The restriction of
neutral pH is a result of the fact that at a high concentration
of H+ cations (low pH), H+ will be competitive against the
incoming cation and thus the exchange of the latter will be
hindered.
Other factors that should be taken into account are the
solid/liquid ratio, which should be low, and the treatment
time, which must be long and combined with renewals of
the solutions (step-by-step ion exchange). In fact, the above
statements are strictly true mostly for the alkali and alka-
line earth element cations, which are practically stable in
aqueous solutions with respect with further hydrolysis re-
actions [60]. Na+ is preferred against the other alkali and
alkaline earth cations, as its homoionic forms are produced
much more easily. Also, Na+ is the most weakly bound ion
in clinoptilolite and thus it is most easily exchanged with
cations from the solution [2830].
Consequently, Na forms of clinoptilolite are expected to
remove other cations easily in ion-exchange applications.
For that reason, Na-homoionic forms are the forms most fre-
quently prepared for research in clinoptilolite literature [23,
31]. Na-homoionic forms are also used for other zeolites,
such as, for example, synthetic Y and A-type zeolites, as
well as for other materials such as bentonite [37,58,61].
It should be noted that in the related literature, exper-
iments are performed in order to study the ion-exchange
behavior of the system and they are not ad hoc studies for
the determination of REC. The latter is measured mainly in
order to analyze the ion-exchange equilibrium results: REC
is compared with MEL to find out if the exchange is par-
 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
tial (REC > MEL) or complete (REC = MEL). It is clear
that if the aim is to study methods for REC measurement,
other cations, such as Cs+ and NH+ 4 , can also be used, since
clinoptilolite exhibits higher selectivity for these cations
than alkali and alkaline earth cations [5]. However, these
cations are not found always to result in higher capacity val-
ues with respect to methods using Na+ solutions [5,62].
The Na-homoionic form of clinoptilolite can be prepared
in batch reactors using concentrated sodium chloride so-
lution (0.52 M), low solid-to-liquid ratio (0.0250.1 g of
clinoptilolite per ml of solution), under high temperature
(6090 C) for a long time period (710 days) and with
periodic (24 h) renewal of the solution. Several batch and
column methods using Na+ treatment for the preparation of
homoionic forms are presented in the literature [8,12,21,29,
38,51,5456,58,59,6366]. Finally, for capacity measure-
ments, the NH+ 4 -form of clinoptilolite has been also used
[52,57,67].
In the case of Na-homoionic clinoptilolite, REC is con-
sidered to be equal to the Na+ content of the material
[8,21,59]. However, the main assumption is that all Na+ is
exchangeable, or in other words, it is not part of zeolite im-
purities [8]. Also, chemical analysis cannot distinguish the
ingoing Na+ amount and the Na+ initially present in the ze-
olite which could be non-exchangeable. Despite the fact that
extensive washings with water can remove the soluble salts,
it is possible that some of these are related to insoluble im-
purities.
For that reasons the following procedure is proposed: af-
ter the preparation of homoionic forms (referred to from now
on as single exchange), the method could be followed us-
ing a second cation (from now on this two-step exchange
will be referred to as double exchange). Considering batch
methods, which are most frequently used, the above steps
are performed using repeated equilibrations. The goal of this
procedure is to re-exchange the cations of the homoionic
zeolite and determine the amount of these cations that is ac-
tually exchangeable.
For the second exchange step, Pb2+ is proposed due
to its superior selectivity, in clinoptilolite, against ions
such as copper, iron, cadmium, chromium, cobalt, nickel,
ammonium, sodium [4,20,6870], barium, strontium, and
cesium [10]. Due to the high selectivity of clinoptilolite for
Pb+ it is found that all the exchangeable cations (96100%)
are exchanged from Na-homoionic clinoptilolites at low
temperatures and low solution concentrations (25 C and
0.010.1 eq/L, respectively) [10,32,59]. Also, Pb2+ was
used for the determination of cation-exchange capacity of
NH+ 4 -clinoptilolite [69]. Despite the fact that high Pb
2+
concentrations could be used to force the system to com-
plete exchange of Na+ , it has been observed that the maxi-
mum exchange level is not a function of solution concen-
tration in Pb+ Naclinoptilolite systems in the range of
0.10.5 eq/L [22]. The same was observed in clinoptilo-
lite cation-exchange capacity using ammonium acetate in
the concentration range of 12 eq/L [67]. Finally, in ca-
75
pacity measurements for natural clinoptilolite using NH+ 4
ions and repeated equilibrations, in the normality region of
0.53 eq/L small differences (<9%) were found without
a specific trend [5]. These results can be explained by as-
suming that higher concentrations of the replacement cation
result in depressing its activity coefficient and in increasing
the difficulty of exchange due to the ionic drift [5].
NH+ 2+
4 can be used instead of Pb , as it has been observed
that in some clinoptilolite samples its uptake is higher than
that of Pb2+ [24,39]. An example of NH+ 4 use is the work of
Barrer et al. for clinoptilolite, where the Na+ content of the
Na-homoionic clinoptilolite, measured by chemical analy-
sis of the material, is considered to be equal to the capacity
of the material since it was found, using ion-exchange tech-
niques with NH+ +
4 ions, that all the Na ions (98%) were
exchangeable [21]. However, for Na-rich clinoptilolite it is
found that the maximum exchange levels for NH+ 4 and Pb
2+
are practically equal (differences of 49%) [35,39]. In an-
other study for Na-rich clinoptilolite, the cation-exchange
capacity measured with NH+ 4 was lower than about 30%
of the maximum exchange level of Pb2+ in the same sam-
ples [10]. It is characteristic that the exchange of Pb2+ with
NH+ 4 initially present in clinoptilolite is irreversible and the
latter is fully replaced by Pb2+ [22]. Concluding, at least
in the case of clinoptilolite, the preference of Pb2+ against
NH+ 4 is well established [4,29,39,59,63,69,71,72].
The basic assumption for REC measurement following
the double-exchange method is that cations other than Na+ ,
which are present in the homoionic form of the zeolite, are in
inaccessible exchange sites (or related to impurities) and do
not participate in the ion-exchange process [8,54]. This as-
sumption seems reasonable considering that the homoionic
forms of zeolites are prepared using concentrated solution
under high temperatures and for long periods of time. Gen-
erally, it is expected that at high temperatures (in the range
of 6090 C) cations located in sites that are difficult to
be accessible at low temperatures can be fully displaced in
equilibrium (capacity) measurements [11,29,57,73]. As de-
scribed earlier, some of the Na+ in the raw material are
possibly related to inactive impurities and thus the REC de-
termination by repeated equilibrations could be lower than
the one derived from chemical analysis. Thus, the REC value
determined by chemical analysis can be considered as an
upper limit of the real capacity of the material, under the
assumption that the exchangeable cations are fully displaced
by Na+ during pretreatment.
4.4.3. Analysis of REC determination methods
Experimental studies found that clinoptilolite content
(% purity of raw zeolite) and exchange capacity exhibit only
a weak linear relationship (R 2 = 0.62) [51]. In Fig. 4
capacity values derived from the related literature are pre-
sented.
The REC values that are above the ideal line can be
explained in the case where the zeolite tuff contains im-
76 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

Fig. 4. Capacity vs purity of clinoptilolite samples (60 capacity values). For ideal line Eq. (4) is used with IEC = 2.16 meq/g (Table 1).

purities that are active. Thus the resulting REC is higher
than the one determined using Eq. (4). Furthermore,
when the REC is calculated only by chemical analysis
of the Na-forms, some Na that are inactive are also in-
cluded in its value. For that reason chemical analysis of
Na-homoionic forms is expected to result in higher val-
ues of REC. The deviation in REC values for the same
purity is the result of the different quality of the impuri-
ties that coexist with the zeolite content. For example,
mordenite exhibits higher capacity than clay impuri-
ties.
REC values that are below the ideal line are suspect of
experimental errors: REC is expected to be equal (in-
active impurities) or higher (active impurities) than the
ideal line values. For example, capacities measured us-
ing the cross-exchange method were found to be lower
than the predicted ones using the ideal line values [5].
According to that study, the cross-exchange method
does not adequately predict the capacity of clinoptilo-
lite, although it works well in the case of phillipsite
and chabazite tuffs. The possible reason is that under
dynamic conditions the exchange is not complete [5].

Table 2
Methods used in the related literature for the determination of REC and purity of the zeolite tuff
Method Cation Double exchange Method for purity Reference
used cation determinationa
Double exchange Na+ NH+4 XRD [51]
Single exchange Na+ XRD [54]
Cross exchange Na+ , K+ XRD [5]
Single exchange Na+ , K+ , NH+
4 XRD [5]
Cross exchange Cs+ , Na+ n.m. [62]
Single exchange Na+ n.m. [8]
Cross exchange (DE)b Na+ NH+4 XRD [72]
Cross exchange Na+ , K+ XRD [24]
Double exchange NH+4 Pb , Na+
2+ n.m. [69]
Double exchange Na+ Pb2+ XRD [74]
Single exchange Na+ XRD [59]
Single exchange NH+4 n.m. [18]
Cross exchange Na+ , K+ n.m. [39]
Double exchange Na+ NH+4 n.m. [21]
Single exchange Na+ XRD [53]
Single exchange Na+ XRD [73]
Cross exchangec NH+4 n.m. [75]
Cross exchange (DE) Na+ NH+4 XRD [76]
Single exchange NH+4 XRD [52]
Double exchange Na+ H+ n.m. [56]
Double exchange Na+ NH+4 n.m. [44]
Double exchange Na+ Pb2+ n.m. [32]
a n.m.: not mentioned.
b DE refers to double exchange, a cross-exchange method followed by a second exchange step, again under dynamic conditions.
c A column method used, referred to as reflux, with saturated ammonium chloride solutions.
 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
Obviously, according to Fig. 4, batch methods (single
and double exchange) are giving the best results. In Ta-
ble 2 the methods used in the related literature for the
determination of the REC and purity of the zeolite tuff
are presented.
4.5. Operating and breakthrough capacities
Operating and breakthrough capacities can be determined
simultaneously using fixed bed reactors. Fixed bed exper-
iments are conducted using vertical columns packed with
zeolite material. The feed is introduced using peristaltic
pumps, at low volumetric flow rates (expressed in bed vol-
umes per hour, BV/h), in upflow mode. Low flow rates in
the range of 510 BV/h were found to be adequate for ion-
exchange applications in columns packed with zeolites [20,
26]. Samples are withdrawn at the exit of the bed at desired
time intervals, depending on the flow rate, and analyzed for
cations. Operating and breakthrough capacities can be eval-
uated by integration using the experimental breakthrough
curves obtained in the column studies [1,20,38,7779]. In
Fig. 5 a typical breakthrough curve is presented.
The operating and breakthrough capacities can be evalu-
ated using the equations
  Veff,T  30 cm) and operated under up-flow conditions [74,81,82].
Veff,T Veff,O X(Veff ) dVeff C0
OC = , (5)
b V0
  Veff,B 
Veff,B Veff,O X(Veff ) dVeff C0
BC = , (6)
b V0
where V eff,O is the effluent volume until the first appearance
of the solute in the exit stream, V eff,B is the effluent volume
until the breakpoint (breakthrough), and V eff,T is the effluent
volume until the exit solute concentration is equal to its in-
let concentration. Breakthrough point is defined as the point
where the exit concentration reaches an upper limit, which
is a portion of the inlet concentration (for example 10%).
The operating capacity is theoretically independent of
the flow rate [1]. However, operating capacity is found to
be flow-rate-dependent and different from that measured in
batch systems [20,25,26]. Thus this kind of capacity is es-
sentially different from and lower in value than MEL [20,26,
Fig. 5. Breakthrough curve.
77
38]. The dependence of OC on contact time has been studied
and modeled in the case of zinc and acid dye adsorption by
bone char and activated carbon, respectively [80]. The fol-
lowing equations were successfully applied,
 
OC = MEL 1 exp(tres ) , (7)
  
OC = MEL 1 exp tres
0.5
, (8)
where t res is the contact (residence) time and is a system-
specific constant. It is obvious that if residence time is in-
finite the operation capacity is equal to the maximum ex-
change level. These observations seem to be a result of the
limiting (low) contact time in fixed beds and of the different
concentration gradients in fixed beds and batch reactors [26].
It must be recognized that batch reactors do not approx-
imate the hydrodynamic and mass-transfer patterns of fixed
bed (column) reactors and probably a partial equilibrium
state in fixed beds is taking place. In addition to that, in
column methods flow may suffer from nonidealities such
as channeling or insufficient wetting of the material. Such
problems may reduce the process efficiency and lead to er-
roneous results in capacity determinations. For this reason
the column should be long enough (typically longer than 20
5. Uses of the several capacity types
Real exchange capacity, as defined in the present paper,
is the amount of all removable cations (counterions) and is
equal (as charge) to the active negative charge of the zeolite
framework [8]. Helfferich uses the total solid concentra-
tion of counterions in the isotopic exchange kinetic models
in order to evaluate the solid diffusion coefficients. Total
solid (and liquid) concentration of counterions (in equiva-
lents) is constant, irrespective of ionic composition, since ion
exchange is a stoichiometric process [1]. Thus, since real ex-
change capacity is essentially equal to the concentration of
counterions (exchangeable cations) of the solid phase, it is
used in batch kinetic models for the determination of ion-
exchange diffusion coefficients [20,21,26,55,83,84].
MEL is a characteristic constant of the specified cation-
exchanger system and it is used in equilibrium studies. For
the construction of isotherms and the processing of equilib-
rium data, the dimensionless solid (Y ) and liquid (X) con-
centrations of the incoming cations are used,
q
Y= , (9)
qref
c
X= , (10)
cref
where c and q are the liquid and solid concentrations of
the incoming cation and cref and q ref are the corresponding
reference values: cref is taken equal to the initial liquid con-
centration and q ref to the capacity of the ion exchanger [77].
78 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879
This capacity is the REC in the case of complete exchange
of the cations initially present in the solid phase. However,
most ion-exchange processes in zeolites are characterized
by partial exchange and thus the exchange level is differ-
ent for different incoming cations and is expressed by the
MEL. Again, REC could be used (the same reference value)
for the construction of isotherms if the aim is to compare the
selectivity of the ion exchanger for different cations. On the
other hand, since a part of REC is not available during par-
tial exchange, MEL should be used (normalized equilibrium
data) in order to evaluate the thermodynamic parameters
of the system, e.g., ion-exchange equilibrium constant and
standard free energy of ion exchange [9,24,32,37], since in
equilibrium the unavailable sites are considered as inactive.
However, this is not true for the kinetic behavior of the sys-
tem. Framework charge (expressed by REC) is influencing
the exchange rate through its electrostatic attraction for the
incoming cations regardless of a partial or a complete ex-
change.
Ideal exchange capacity can be used only to compare pure
zeolite species. In the case of zeolite tuffs containing im-
purities or other minerals TEC is an overestimation of the
exchange ability of the material due to the fact that some of
the zeolite tuff cations are part of impurities or they are not
available for ion exchange [10,13,14].
The operating capacity is used in fixed bed ion-exchange
models, as it is expressing the part of MEL that is available in
the specific column operation [26]. Finally, breakthrough ca-
pacity is used for the determination of selectivity series and
for the design of column operations [1,38,84]. Breakthrough
capacity is dependent on a number of experimental condi-
tions and by this point of view is similar in nature to effective
capacity. Similarly, effective capacity (EC) is completely de-
pendent on the experimental conditions; it can only be used
in order to have a rapid indication for the ion-exchange sys-
tem and it is also useful when comparing a large number of
different ion-exchange materials [13,55]. BC and EC could
be helpful during the first steps of design and evaluation of
ion-exchange operations.
6. Conclusions
In the present paper seven different types of capacity are
examined: ideal exchange capacity, theoretical exchange ca-
pacity, effective capacity, real exchange capacity, maximum
exchange level, operating capacity, and breakthrough capac-
ity. Capacity types are distinguished theoretically and exper-
imentally and their specific uses are described. This work
can be considered as a first step toward a unified terminol-
ogy and the development of standard methods in the field
of zeolite capacity, as several subjects have to be theoreti-
cally analyzed and experimentally verified. Among others,
the determination of the concentration of the exchangeable
cations of the solid phase, defined here as real exchange ca-
pacity, is considered to be the most important and difficult
task since several impurities are usually present in natural
zeolites and experimental errors can mask its accurate deter-
mination. Another problem is that in some cases metals are
not only exchanged but also adsorbed or precipitated onto
the solid surface. In this case the zeolite capacity is the sum
of the active ion exchange and adsorption sites.
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