Mineral.
Dcposita 31,554 562 (1996)
Ion exchange equilibria in zeolite minerals
C. Colella
Dipartimcnto di lngegneria dei Materiali e della Produzione, Universit,~ di Napoli Federico 1I, Piazzale V. Tecchio 80, 80125 Naples, Italy
Received: 30 November 1995/Accepted: 10 April 1996
Abstract. C a t i o n exchange equilibria of the m o s t c o m -
m o n s e d i m e n t a r y zeolites are reviewed. Selected exchange
isotherms a n d t h e r m o d y n a m i c e q u i l i b r i u m c o n s t a n t s are
r e p o r t e d a n d interpreted in terms of selectivity of one
cation over another. Selectivity sequences of various
zeolites are c o m p a r e d with each other in the light of
Eisenman's theory a n d utilized to predict or explain speci-
fic practical performances.
Zeolites are the m o s t i m p o r t a n t i n o r g a n i c cation ex-
changers. N o w a d a y s they c o m p e t e with cation exchange
resins in water processing (softening) a n d in purification of
w a s t e w a t e r and sewage. O r g a n i c resins are usually prefer-
red for their greater cation exchange capacity, higher
reaction rates and better resistance to chemically aggres-
sive environments. Zeolites on the c o n t r a r y show higher
cation exchange selectivities, g o o d resistance to temper-
ature a n d ionizing radiations, a n d excellent c o m p a t i b i l i t y
with the environment. Since zeolites are widely used in
m o d e r n t e c h n o l o g y as selective adsorbents, m o l e c u l a r
sieves and p a r t i c u l a r l y as catalysts, ion exchange p r o p e r t y
is e m p l o y e d also as a tool for tailoring the structure in
o r d e r to o b t a i n specific performances.
A p a r t from the use as a "builder" in detergent formula-
tion, for which a synthetic zeolite, N a - A , LTA, has p r o v e d
to be the most effective so far (Schwuger and S m o l k a
1976), m a n y of the actual or potential a p p l i c a t i o n s of
zeolites as ion exchangers in industrial, agricultural
a n d / o r e n v i r o n m e n t a l fields involve the use of n a t u r a l
materials of diagenetic origin ( G o t t a r d i 1989). This mainly
d e p e n d s on e c o n o m i c considerations, but specific p r o p e r -
ties, such as selectivity for noxious and toxic species, have
also been g o o d reasons for using these minerals. A great
deal of research on n a t u r a l zeolite ion exchangers has been
focused on the most c o m m o n l y occurring types, especially
clinoptilolite, m o r d e n i t e a n d chabazite.
For the sake of clarity, zeolite structure types, when necessary, are
referred to throughout the text by the structure type codes, assigned
by the Structure Commission of the International Zeolite Associ-
ation (Meier and Olson 1992).
MINERALIUM
DEPOSITA
9 Springer-Verlag 1996
This study aims at surveying the f u n d a m e n t a l s of ion
exchange equilibria with reference to the most widespread
n a t u r a l zeolite types, whereas aspects connected with en-
v i r o n m e n t a l a p p l i c a t i o n s are considered in a n o t h e r work
within this v o l u m e (Pansini 1996).
Historical perspective
Ion exchange phenomena have been observed, especially in agricul-
ture, since the dawning of civilization. The ancient Greeks knew that
the passage of brackish waters through certain "sands" resulted ill
the modification of their "chemical" features (Helfl'erich 1962).
Nevertheless it was not until the middle of the nineteenth century
that the scientific bases of ion exchange were investigated and
disclosed. Thompson (1850) and Way (1850) discovered that ammo-
nia from a fertilizer dissolved in water could be fixed by a soil bed
during percolation, substituting for calcium released in the eluate.
Later on. this behaviour was attributed to the presence of clay
minerals and humic acids in the soil. This property was named "base
exchange" and this denomination was preserved for a long time, so
that it was even used in the late 1930s, for instance in Hey's defini-
tion of zeolite (Hey 1937).
An important advance in the understanding of ion exchange
phenomena was accomplished by Eichhorn (1858), who in his pion-
eering study of ion exchange in zeolites pointed out the reversibility
of this type of reaction.
Utilization of natural ion exchangers as industrial materials
was not considered advantageous for a long time. Zeolites, before
the discovery in the 1950s of the enormous deposits of zeolite-
bearing rocks in many parts of the world, e.g. Japan, Italy,
United States, were believed to be nothing more than simple
mineralogical curiosities. That is why the first important industrial
application of ion exchange involved the permutites, a class
of partially crystalline synthetic aluminosilicate exchangers
widely employed, especially for water softening, in the early decades
of this century (Gans 1905). After 1935 the attention of the industrial
world was attracted by the newly discovered ion exchange resins
(Adams and Holmes 1935), which in a few years became the
main product for solving problems related to water softening and
deionization.
A renewal of interest in inorganic ion exchangers in the early
1950s was connected with the birth and growth of the nuclear
industry, and the need to find suitable ion exchangers for processing
radionuclide-containing waters. This stimulated fundamental re-
search on inorganic ion exchangers, pointing out their elevated
selectivity in general, and specificity for certain ions, and opening the
 555

way for applications in metal recovery from exhausted solutions,

wastewater treatment and aquatic pollution control.
As far as zeolites are concerned, systematic studies on ion ex-
change properties of either natural or synthetized zeolites were
initiated in the same period in England by Barrer (1950).

Phenomenology of ion exchange

The ion exchange reaction occurs between two or more phases, one F---?--- -7-
/ / /!,/
-< - ...... 7-
/
of which is liquid (solution or melt), which exchange two or more
ions (cations or anions), more or less strongly bound to each phase.
Ion exchange is commonly an equilibrium reaction, but there are
a few cases in which exchange proves to be irreversible. The quantity
I / VF
of ions exchangeable by a solid exchanger, depending on its chemical
and structural features, is called the ion exchanye capacity and is
usually expressed in milliequivalents/g.
,iii
In the simplest occurrence of ion exchange two phases are in-
volved, the solid and the liquid, which compete in mutually sharing
two ions. Ion transfer from one phase to the other is subject to the /" i
observance of electroneutrality and regulated by the ion concentra-
tion in both phases and selectivity, here referred to as the measure of o ~-M
the preference that the exchanger exhibits for one ion compared with
the other. This parameter is a function of both the energy of ion- Fig. 1. Schematic isotherms, showing unselective (a) and selective (b)
lattice interaction and the hydration energy (ion-solution interac- behaviour of the exchanger for the incoming ion M, or exhibiting
tion). a selectivity reversal (c). EM, equivalent fraction of M present at
In zeolites, ion exchange arises from the presence of extra-frame- equilibrium in the liquid phase; E~t, equivalent fraction of the same
work cations, located in the regular array of channels and cages, ion in the exchanger. Arrows indicate the reversibility of the ex-
which constitute the rigid anionic framework. Cations are bound to change reaction. The quotient (area 1)/(area 2) measures the separ-
the lattice and to water molecules, which normally fill the zeolite ation factor e at the point P (see text)
micropores. When the zeolite comes into contact with an electrolytic
solution, the zeolitic cations can be removed from their sites and
replaced by other cations fiom the solution. Substitution is
stoichiometric and, provided that suitable experimental procedures
are set up, it can be exhaustive, i.e. it can cover the entire cation EM
exchange capacity (CEC), unless partial or total exclusion occurs,
due to inaccessibility of specific exchange sites. Actually, in the
zeolite structures there are commonly various cation sites, which
differ from each other in framework position and therefore in bond
energy. This may affect both the extent and kinetics of cation
exchange. Incomplete exchange reactions may arise from cation
sieving. This may be due to cation size, both in diameter or in
////////
volume, being incompatible with the channel dimensions or with the
space available in the specific site. Cation sieving may also occur due
to the inability of the negative charge distribution on the zeolite
structure to accommodate a given cation (Dyer 1988).

Ion exchange equilibria in zeolites /A/ /

A cation exchange reaction m a y be written as

n M (s)
m+ -}- m N "(z)+ +~- n M m
(z)+ + m N "(s)+
where m a n d n are the valences of exchanging cations
M a n d N a n d subscripts s a n d z denote solution a n d
zeolite phase, respectively.
E x p e r i m e n t a l e q u i l i b r i u m data, at a given t e m p e r a t u r e
a n d at c o n s t a n t total ion n o r m a l i t y in solution, are usually
plotted in such a way as to o b t a i n the cation e x c h a n g e
isotherm, a curve which is a suitable tool for a n immediate
e v a l u a t i o n of the zeolite selectivity for one cation (M) over
a n o t h e r (N). By c o n v e n t i o n , the isotherm reports the
equivalent fraction of the i n c o m i n g cation, EM, present at
e q u i l i b r i u m in the liquid phase, against the equivalent
fraction EM of the same cation in the zeolite. However, it is
to be r e m e m b e r e d that, by definition, both EM + EN = 1
a n d EM + EN = 1. It is n o t e w o r t h y that e q u i l i b r i u m data,
(1)
0 g-'M
Fig. 2. Schematic isotherms, showing unselective (d) and selective (e)
behaviour of the exchanger for the incoming ion M with clear limits
to accommodate the ion in the framework. Curves f are indicative of
a hysteresis loop with a phase separation. Co-ordinates and arrows
as in Fig. 1
a n d therefore the isotherm profile, in the case of uni-
divalent cation exchange depend, n o t only on the temper-
ature b u t also o n the total ion c o n c e n t r a t i o n in the liquid
phase.
A l t h o u g h a generalization is not possible, four kinds of
profiles are usually observed for the cation exchange iso-
therms (Figs. 1, 2):
556
1. The curve is completely over (Fig. la) or under (Fig. lb)
the diagonal of the diagram, which means that the
zeolite is unselective or selective for the incoming ca-
tion M, respectively;
2. The curve is a sigmoid crossing the diagonal at one
point (Fig. lc), which indicates a selectivity reversal, as
a function of EM;
3. The curve shows a clear unselectivity (Fig. 2d) or select-
ivity (Fig. 2e) for the cation M, but the exchange is not
complete, i.e. only a fraction of the CEC is available for
M;
4. The curve presents a hysteresis loop (Fig. 2f), which
means that in a given range of EM there are two solid
phases in equilibrium with the solution.
Curves of type I may indicate that in the zeolite struc-
ture there is only one site group, but this occurrence is
rather rare, and is evidenced by the absence of inflections
in the isotherm, i.e. the experimental curve approximates
a rectangular hyperbola. The presence of inflections in the
isotherm, which may occur in curves of any type, is an
indication that in the zeolite structure there are two or
more site groups. Isotherms of type 3 show an evident
limit in the occupancy of all the available cation sites. This
may be due to ion sieving or volume exclusion phenomena
(see the previous section). In case 4 the progressive loading
of the cation M in the zeolite structure results in a phase
separation over the composition range corresponding to
the hysteresis loop.
When the isotherm exhibits a concave profile, e.g.
curves b and e in Figs. 1 and 2, the uptake of the incoming
cation M by zeolite from solution usually follows a Lang-
muir-type isotherm, which in its simplified expression,
valid particularly when M and N are singly charged and
the zeolite is unselective for N, may be written
bQmaxCM (2)
QM - 1 + bCM
where Q,u is the amount of M m+ in the solid phase per unit
weight of zeolite, Q.... is the maximum value for Q:u, CM is
the equilibrium concentration of M m+ in the solution, and
b is the Langmuir constant. For convenient application to
experimental data Eq. (2) may be written in a linear form,
for instance:
QM
- bQm~x - bQM (3)
C,u
so that from a plot of QM/C.~ versus Q~, one can
obtain Q...... which is the maximum loading of M on the
zeolite.
The analysis of the equilibrium data according to the
Langmuir-type equation is possible also when the cations
M and N have unequal charges and are in competition
with each other, i.e. zeolite exhibits comparable selectiv-
ities for both of them (Boyd et al. 1947; Mimura et al.
1992).
Processing of equilibrium cation exchange data allows
us to obtain some other useful parameters characterizing
the exchange reaction, e.g. the separation factor, 7, which
is a measure of the preference of the zeolite for the cation
M over N at a given E.u. This may be calculated from the
expression
/~M EN
u. = _ (4)
E,~,Eu
or obtained by a graphical evaluation from the cation
exchange isotherm. For instance the value of :r related to
the point P in Fig. 1, is given by the ratio (area l)/(area 2).
The separation factor cannot be considered as a measure
of the selectivity, because it varies as a function of the
composition of both the solid and liquid phases at the
equilibrium. A comprehensive estimation of selectivity can
result from the knowledge of either the thermodynamic
equilibrium constant, K , , or the standard free energy of
exchange, AG o, defined as
m- n
ONaM
K,, - n - ttl
(5)
a M (l N
RT
AG O - In K , (6)
Hm
where a and h are the activities of the cation in either the
solution or the zeolite, respectively. It has to be observed
that K,, and AG o values give unequivocal indications as
regards selectivity only for type a/b isotherms (Fig. 1) and
generally for low zeolite loadings (low E u values). Other-
wise, the indication may be misleading, in that it reflects
contrasting behaviours over the whole composition range,
for instance possible selectivity reversals (Fig. lc).
The value of K,, can be calculated from the equilibrium
cation exchange data using an integration procedure
derived by Gaines and Thomas (1953), provided the
activity coefficients of the cations in the liquid phase can
be estimated accurately. A commonly used activity coef-
ficient expression for dilute electrolytes is given by
Glueckauf (1949), although other expressions exist for
more concentrated solutions. A comprehensive descrip-
tion of the procedure for obtaining the thermodynamic
quantities connected with cation exchange reactions
involving zeolites may be found in several papers
(Townsend 1986; Grant and Fletcher 1993; Pabalan 1994:
Caputo et al. 1995).
Studying a certain number of cation exchange equilib-
ria in a given zeolite type allows us to learn the specific
selectivity sequences (Sherman 1978), which are very use-
ful in predicting the zeolite behaviour in any practical
application. Actually the allowed selectivity sequences in
a set of cations are much less numerous than expected
from the large number of permutations which are math-
ematically possible. This is due to some thermodynamic
restrictions, which, at least in the most favourable cases,
can be predicted by theory. Starting from a simplified
cation exchanger model, considering the electrostatic in-
teractions of cations with the negatively charged exchange
sites on the framework and with water molecules in solu-
tion, Eisenman (1962) was able to predict that only 11
selectivity sequences out of 120 that are theoretically pos-
sible were allowed for uni-univalent cation exchanges
in the group of the alkali metals (Li, Na, K, Rb, Cs).
Sherry (1969) extended the treatment to divalent cations,
predicting 7 sequences out of 24 possible for di-divalent
 557

exchanges in the group of the alkaline earth metals (Mg,
Ca, Sr, Ba).
According to Eisenman (1962), the behaviour of a ca-
tion exchanger, and therefore of a zeolite, in an uni-
univalent cation exchange depends on the anionic field
strength exhibited by the solid. In the case of a low field
strength, presented by the most siliceous zeolites, cations
with lower charge density, such as Cs, are preferred, so
that the selectivity essentially depends on the difference in
the free energy of hydration of the two cations in competi-
tion, more than on the difference in electrostatic interac-
tion of the cations with the framework. On the contrary, it
is predictable that the aluminous zeolites, characterized
by high field strengths, tend to prefer cations with higher
charge density, for instance Li and Na. In this case select-
ivity is controlled more by zeolite (cation-framework in-
teraction) than by solution (cation-water interaction).
With reference to di-divalent cation exchange, zeolites,
irrespective of their composition, always behave as weak-
field-generating cation exchangers (Sherry 1969). Accord-
ingly, they tend to prefer in any case the large cations, such
as Ba. Finally, in the case of uni-divalent exchange, alumi-
nium-rich zeolites evidence a marked preference for
divalent cations, but this tendency can be reversed in the
case of more siliceous zeolites (Sherry 1969).
Natural zeolites as ion exchangers
Table 1 summarizes the chemical compositions and the
cation exchange capacities of the most important natural
zeolites. The types taken into consideration are known to
occur either as hydrothermal minerals or as species of
diagenetic origin, constituting deposits of actual or poten-
tial commercial interest (Deffeyes 1968; Hawkins 1984).
In the following, the main features of these natural
zeolites in cation exchange equilibria involving some
groups of cations will be presented and discussed.
Alkali and alkaline earth cations
Tables 2 and 3 summarize the exchange properties of
some natural zeolites towards alkali and alkaline earth
cations in terms of the selectivity sequences found experi-
mentally, compared with the patterns predicted by theory
(Eisenman 1962; Sherry 1969). In the case of incomplete
experimental sequences, the assigned selectivity series ref-
erence numbers appear in parentheses. Uncertainty is
indicated by the alternative of two or more numbers.
Although there are some irregularities, it is evident that
the natural zeolites under consideration prefer the cations
with large radius in accordance with theory (see the pre-
vious section), whereas the smaller cations tend to be
preferred by the aqueous phase. This is the typical behav-
iour of the low-field-strength ion exchangers. The effect on
the selectivity of increasing A1 content in a zeolite series is
demonstrated in the two H E U structural types (Table 2).
In fact, clinoptilolite, characterized by a higher silicon
content, exhibits a low-field selectivity pattern (I), while
heulandite with a lower silicon content shows a stronger-
field pattern (IIIa/IV).

Table 1. Chemical composition and cation exchange capacity of some natural zeolites
Zeolite Structure Idealized unit-cell formula CEC a Si/A1 ratio
type code meq/g reported ranges b
Chabazite CHA Ca6 [Al12Si24Ov2] 940H20 3.86 1.43 4.18
Clinoptilolite c HEU Na3K3 [A16Si3oO~2] 920H20 2.22 2.92 5.04
Erionite ERI Na2K/MgCal.s[A19Si27OTz]'27H20 3.16 3.05 3.99
Ferrierite FER Na2Mg2 [A16Si30072] " 18H20 2.33 3.79-6.14
Heulandite r HEU Ca4[A18Siz8072 ] "24HzO 2.91 2.85 4.31
Laumontite LAU Ca4 [A18Si16O~8] 916H20 4.25 1.95 2.25
Mordenite MOR Na8[AlsSi40096 ] "24H20 2.29 4.19 5.79
Phillipsite PHI NazK2Ca[AI6Si16032 ] 912H20 4.49 1.45 2.87
aCation exchange capacity calculated from the idealized unit-cell formula
bData after Gottardi and Galli (1985)
These are two isotypic zeolites, differing from each other in chemical composition (Mason and Sand 1960; Boles 1972; Alietti 1972) and/or in
thermal behaviour (Mumpton 1960)

Table 2. Selectivity patterns of alkali cations exhibited by some natural zeolites

Zeolite Selectivity series Literature reference Eisenman's series
reference numbera
Chabazite Cs > K > Rb > Na > Li Barrer et al. 1969 IIa
Clinoptilolite Cs > Rb > K > Na > Li Chelishev et al. 1973 I
Erionite Rb > Cs >~K > Na > Li Sherry 1979 II
Ferrierite Cs > Rb > K > Na Ahmad and Dyer 1988 [I]
Heulandite K > Rb > Na > Li Filizova 1974 IIIa/IV
Mordenite Cs > Rb ~ K > Na > Li Ames 1961; Rao and Rees 1966 I/lIa
Phillipsite Cs > K > Rb > Na > Li Barrer and Munday 1971 IIa
" See Eisenman (1962)
558

Table 3. Selectivity patterns of alkaline earth cations exhibited by some natural zeolites

Zeolite Selectivity series Literature reference Sherry's series

reference number"

Chabazite Ba > Sr > Ca > Mg Ames 1961; Barrer et al. 1969 I

Clinoptilolite Ba > Sr > Ca > Mg Ames 1961; Filizova 1974 1
Erionite Ba > Sr > Ca > Mg Ames 1961; Sherry 1979 1
Ferrierite Ba > Sr > Ca > Mg Ahmad and Dyer 1988 I
Heulandite Sr > Ba > Ca Filizova 1974 unpredicted
Mordcnite Ba > Sr > Ca > Mg Ames 1961 I
Phillipsiteh Ba > Sr > Ca Barrer and Munday 1971 [1]

See Sherry (1969)

b Exchange for Ba has proved to be irreversible (Barter and Munday 1971)

Table 4. K, values for Na -+ Cs and 2Na -* Sr exchanges in natural 1.0

zeolites at 25 C
a
Ec~
Zeolite NarCs Reference 2Na~Sr Reference

Chabazite 69.2 ~ 0.883 "

51.0 h 0.159 t,
Clinoptilolite 51.9 ~ 1.290
55.8 d 0.321 ~
Erionite 32.9 ~ 0.794
Ferrierite~ 8.0 ~ 0.074
Mordenite h 27.2 ~ 0.5
Phillipsite 24.2 i 0.066 J
26.4 ~ 0.107

"Equilibrium data obtained at 50 C Barrer et al. 1969)

u Equilibrium data obtained at 23 ~C Perona 1993)
Ames (1965a)
d Equilibrium data obtained at 30 C Howcry and Thomas 1965)
~Pabalan et al. 1993
rThe K, values have been calculated from the reported AG * values
through the application of Eq. (6) and making use of the triangle rule
(Barrer and Klinowski 1974) 0.5 Ecs 1.0
g Equilibrium data obtained at 24 C (Ahmad and Dyer 1988)
h Synthetic mordenite (Zeolon by Norton) Fig. 3. Ion exchange isotherm protiles at 25 C for the pair N a r C s
~Barrer and Klinowski 1974 on various zcolites at 0.1 total normality: (a) chabazite (Barrer et al.
J Barrer and Munday 1971 1969); (b) phillipsite (Barrer and Munday 1971); (c) erionite (Sherry
1979). Coordinates as in Fig. 1

A m o n g the various equilibria investigated, p a r t i c u l a r
a t t e n t i o n has been paid to those involving cesium and
s t r o n t i u m for the possible practical implications, i.e. 13Yes
a n d 9~ r e m o v a l from w a s t e w a t e r of nuclear p o w e r
plants.
As far as cesium is concerned, the d a t a in Table 2 indic-
ate that m o s t n a t u r a l zeolites, n a m e l y chabazite, clinop-
tilolite, ferrierite, m o r d e n i t e and phillipsite, exhibit
a s t r o n g preference for this cation. A high selectivity for
cesium has been claimed also for l a u m o n t i t e ( R o m a n -
tschuk et al. 1966). This o b s e r v a t i o n is confirmed by the
profiles of the relevant i s o t h e r m s (see Fig. 3) and especially
by the values of the c o r r e s p o n d i n g t h e r m o d y n a m i c equi-
librium c o n s t a n t s (Table4). D i s c r e p a n c y of d a t a in
T a b l e 4, c o n c e r n i n g the same zeolite type, m a y be due to
the use of a different activity coefficient m o d e l for the
a q u e o u s solution a n d p a r t l y to the use of a different zeolite
material. Actually, it has been d e m o n s t r a t e d , in a c c o r d -
ance with E i s e n m a n ' s ion exchange model, that isostruc-
tural zeolites with a different silica to a l u m i n a ratio a n d
therefore with a different f r a m e w o r k charge density m a y
exhibit m a r k e d l y different cation exchange features and
t h e r m o d y n a m i c quantities (Barrer a n d K l i n o w s k i 1972;
Shibue 1981). (Note that f r a m e w o r k charge density, which
is a m e a s u r e of the anionic field strength, equals the
n u m b e r of AI a t o m s (p.u.c.) x charge on electron/unit cell
volume ( O ' C o n n o r a n d T o w n s e n d 1985).
In c o n t r a s t to their g o o d selectivity for cesium, n a t u r a l
zeolites do not show a great preference for s t r o n t i u m
(Table 4 a n d Fig. 4). This is mainly due to the low-field
strength exhibited by the silicon-rich n a t u r a l zeolites.
T h a t is why the best p e r f o r m a n c e in the j o i n t r e m o v a l of
Cs and Sr from nuclear p o w e r p l a n t w a s t e w a t e r is to be
expected fi'om mixtures of n a t u r a l zeolites and alumi-
nium-rich, strontium-selective synthetic zeolites, such as
zeolite N a - A , E T A (Ames 1962).
Ammonium
A great deal of research has been carried out in the last
thirty years on the c h a r a c t e r i z a t i o n of n a t u r a l zeolites as

1.0
Esr
0.5
0 0.5 Esr 1.0
Fig. 4. Ion exchange isotherm profiles for the pair Na~Sr on
various zeolites at 0.1 total normality: (a) chabazite at 50~ (Barter
et al. 1969); (b) phillipsite at 25 :'C (Barrer and Munday 1971); (c)
erionite at 25 ~ (Sherry 1979) Coordinates as in Fig. 1
possible means for removing ammonia from water. This
subject was introduced by Ames (1967) in a report which
presented the remarkable selectivity of several zeolites, e.g.
clinoptilolite, for ammonium. Further investigations con-
firmed this observation also from a quantitative point of
view (Bilba et al. 1983; Suzuki and Ha 1984). Howery and
Thomas (1965) found a Ka value of 8.53 at 30 ~ for the
N a ~ N H 4 equilibrium in clinoptilolite, while Townsend
and Loizidou (1984) obtained a value of 5.12 at 25 ~
Several other natural zeolites have been considered for
equilibrium studies involving ammonium. Remarkable
selectivities for this cation have been observed in particu-
lar for chabazite, ferrierite, mordenite and phillipsite.
K, at 25 ~ for the Na --* NH4 exchange in chabazite was
found to be 5.32 (Barrer et al. 1969). The same value for
ferrierite at 24 ~ mordenite at 25 ~ and phillipsite at
20~ proved to be 2.58 (Ahmad and Dyer 1988), 6.43
(Townsend and Loizidou 1984) and 13.26 (Garcia Her-
nandez et al. 1994), respectively.
Equilibrium exchange data on clinoptilolite at 23 ~ for
several cation pairs, including ammonium and the most
common alkali and alkaline earth cations found in natural
waters, are summarized in the isotherms of Fig. 5 (Sher-
man 1978). The following selectivity sequence is easily
deduced:
K > NH 4 > Na > Ca > Mg.
It is noteworthy that the same pattern, apart from the
possible inversion of potassium with ammonium, is exhib-
ited by several natural zeolites, such as chabazite (Barrer
et al. 1969), mordenite (Hagiwara and Uchida 1978; Czar-
an et al. 1986) and phillipsite (Sherman 1978), which
accounts for the preferred exchange of the zeolites with
lower field strengths for cations having a low charge
density (Eisenman 1962; Sherry 1969). The thermodyn-
amic data referred to here, complemented by the CEC
559
1.0
ENH4
0.5!
[
0 0.5 ENH4 1.0
Fig. 5. Isotherm profiles for the exchange of ammonium for various
cations on clinoptilolite at 0.1 total normality and 23 ~ (Sherman
1978). Coordinates as in Fig. 1
values reported in Table l, are consistent with the obser-
vation that phillipsite exhibits the best performances in
ammonium removal from model solutions containing also
sodium, potassium, calcium and magnesium (Sherman
1978).
All these data depict a very favourable situation for
actual or potential applications in industrial and agricul-
tural wastewater purification, aquaculture, animal feed-
ing, agriculture and horticulture (use of natural zeolites as
nitrogen fertilizers).
Heavy metal cations
Natural zeolites, such as those reported in Table 1, fre-
quently display good selectivities for heavy metal cations,
which makes them valuable tools for the purification of
industrial wastewater and/or metal recovery from process
water. The literature contains numerous papers on ap-
plications (Pansini 1996), whereas data on cation ex-
change equilibria involving heavy metal cations and natu-
ral zeolites are scarce, sometimes conflicting, and often
poorly comparable with each other. In general it is con-
firmed, in agreement with Eisenman's theory (Eisenman
1962; Sherry 1969), that natural zeolites, pre-exchanged in
sodium form, are fairly selective for monovalent heavy
metal cations, provided these are characterized by low
charge densities. As regards divalent cations, selectivity is
predominantly determined by their hydration energies
more than by the cation-lattice interaction. Accordingly,
natural zeolites tend to prefer cations with lower hy-
dration energy, e.g. lead over cadmium.
The cations for which thermodynamic data are avail-
able in the literature are Ag +, Cd 2+, Pb 2+, and T1 +.
A good selectivity for silver is demonstrated by chaba-
zite (Barrer et al. 1969; Barrer and Sammon 1955) and
560
clinoptilolite (Gradev et al. 1988), which opens the way to
their use in silver recovery from the wastewater from
photographic production. In particular, K,, at 25 C for
Na ~ Ag exchange in chabazite was found to be 11.4
(Barrer et al. 1969). Also the selectivity sequences exhib-
ited by both zeolites are very similar: K > Ag > NH4 >
Pb > Na > Ca > Li for chabazite (Barrer et al. 1969) and
K > NH4 > Ag ~> Pb > Na > Ca > Li for clinoptilolite
(Czaran et al. 1986). Data on Na --+ Ag exchange in fer-
rierite are also available in the literature (Ahmad and
Dyer 1984; 1988).
Calculated K~, values for 2Na --+ Cd exchange in several
natural zeolites are usually < I (Caputo et al. 1995; Loi-
zidou and Townsend 1987a), although favourable values
of the separation factor (~ > 1) have sometimes been found
for low Cd loadings on chabazite and phillipsite (Colella
et al. 1995). Based on the Ka values at 25"C and 0.1 N
total cation concentration in solution, the decreasing sel-
ectivity pattern of the investigated zeolites for Cd appears
to be (Caputo et al. 1995; Loizidou and Townsend 1987a):
CHA > MOR > FER > HEU (clinoptilolite) > PHI.
Natural zeolites appear to be usually very selective for
lead (Loizidou and Townsend 1987b; Pansini et al. 1996).
K,, values for the Na-Pb pair turn out to be very high
especially for mordenite, phillipsite and clinoptilolite. Sel-
ectivity follows the sequence: MOR > PHI >~ CLI >
CHA. The 2Na ---, Pb exchange on ferrierite proved to be
irreversible (Loizidou and Townsend 1987b).
A remarkably high selectivity of Na-exchanged
chabazite for T1 has been found (K,, = 83.5 at 25 r'C)
(Barrer et al. 1969). Ferrierite also demonstrates a good
selectivity for this cation (Ahmad and Dyer 1988).
Cation exchange isotherms of Cu exchange on
chabazite (Barrer and Sammon 1955) and clinoptilolite
(Semmens and Seyfarth 1978; Blanchard et al. 1984; As-
senov et al. 1988), Co exchange on clinoptilolite (Blanc-
hard et al. 1984), Zn exchange on clinoptilolite (Semmens
and Seyfarth 1978; Blanchard et al. 1984; Assenov et al.
1988) and Cr exchange on phillipsite and chabazite
(Pansini et al. 1991) are also reported in the literature.
With reference to the latter cation, it is worth noting the
irreversibility of its exchange on both phillipsite and
chabazite. The chabazite structure in particular undergoes
a marked breakdown owing to Cr exchange. Both phe-
nomena, cation exchange irreversibility and structure
breakdown, should be connected to the structure distor-
tion resulting from the substitution in the zeolite frame-
work of one trivalent cation in place of three monovalent
cations.
Rare earth cations
Attempts to introduce rare earth cations into the zeolite
framework have been made since the 1950s. This is of
interest for two reasons. Firstly, zeolites might be utilized
for decontaminating radioactive liquid wastes containing
lanthanides, e.g. cerium, or actinides, e.g. thorium. Sec-
ondly, cation exchange might be used for preparing het-
erogeneous catalysts, such as La-exchanged zeolite cata-
lysts, exhibiting improved thermal and chemical stabilities
over the pure H-forms (Lee and Rees 1987).
Exchange for rare earths is favoured in zeolites with
high framework charge density. In fact, these can more
easily accommodate cations with very high charge densit-
ies, satisfying with one cation three or more anionic sites
better in zeolite frameworks.
Natural zeolites, such as those reported in Table 1, are
usually characterized by a medium-low framework charge
density. That is why the exchange of natural zeolites for
rare earth cations has been often unsuccessful, e.g. the
3Na ~ La exchange in chabazite (Barrer and Sammon
1955), or the exchange for Ce in erionite, phillipsite and
clinoptilolite (Ames 1965b). Cation exchange of either
clinoptilolite or mordenite for Th has recently been dem-
onstrated to be possible, although unfavourable (Con-
stantopoulou et al. 1994). Only partial exchange has been
achieved and a low selectivity has been shown. The value
of K,, at 25 C and 0.01 total normality for the pair Na-Th
on clinoptilolite and mordenite has been found to be
0.0046 and 0.0017, respectively.
Conclusions
Ion exchange is the only technological sector in which
natural zeolites may compete in terms of performance
with the commercial synthetic zeolites. Actually, dia-
genetic zeolites characterized by medium-high Si/AI ratios
do not replace, but complement, commercial types, such
as zeolites A, LTA and X, FAU, which are more alumi-
nous. In other words natural and synthetic zeolites have
different fields of application as cation exchangers.
As has been pointed out in this review study, in
agreement with Eisenman's theory, supported by experi-
mental confirmation, zeolite selectivity for a given
cation depends on its anionic field strength (or frame-
work charge density) and this feature is determined in
turn by the relevant Si/A1 ratio. This means that, at
least in principle, natural zeolites are irreplaceable
in many specific applications. The possible removal
from wastewater of ammonium, cesium and many heavy
metals, such as lead, are good examples of this mentioned
specificity.
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