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9 Ion Exchange in Zeolites

By L. V. C. REES
Physical Chemistry Laboratories, Imperial College of Science and Technology.
London, S.W.7

1 Introduction
The subject of ion exchange in zeolites has not been covered in any previous
Annual Report. This report will, therefore, not be limited to papers published
in the past year but will include the significant papers of recent years. This topic
has been studied for well over a hundred years mainly because of the importance
of zeolites in the chemistry of soils. R. M. Barrer has studied the fundamental
aspects of zeolite chemistry for over thirty years and contributed greatly to our
understanding of this subject. The great upsurge, however, in the publication of
papers on the various aspects of the chemistry of zeolites occurred after the
discovery in 1959-62 of the catalytic activity of zeolites in various processes
used by the petroleum refining industry. Just prior to this discovery Union
Carbide Corporation, U.S.A. had developed methods for the production of
Linde Molecular Sieves on a commercial basis. These two factors have led to
the virtual monopoly in the use of zeolites as catalysts in petroleum cracking.
In the production of specific catalysts ion exchange processes are required.
Much interest has, therefore, developed in the structure, position of the cations,
and the fundamental aspects of ion exchange in these materials.
In 1967 the first international conference on zeolites was held in London.
This was a successful venture and the second conference has recently taken place
in Worcester, Massachusetts, U.S.A., where a decision was taken to hold
subsequent meetings every three years. The next one, in 1973, will be held in
Zurich.

2 Structure of Zeolites
In order to analyse ion exchange, catalytic, heats of sorption, and various other
results it is essential to know the framework structure, and the location of cations
and water molecules in these materials. Many papers have been published on
the more catalytically interesting structures and the most recent papers of
interest can be summarised as follows.
X, Y, and Faujasite.-These zeolites are the ones most widely used as catalysts
and much work has been reported on their structures. Zeolites X and Y are
synthetic forms of an alumino-silicate framework which has the same topology
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192 L. V . C. Rees
as that of the natural mineral called faujasite. The Si, A1 content of Y is similar
to that of faujasite whereas X is much more aluminous. Since one equivalent of
cation is required per mole of Al. zeolite X has a higher cation density than
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faujasite or zeolite Y.
The framework structure is classified,’ a stereogram presented,2 and the
T-0 distances and T-0-T angles (where T = Si or Al) tabulated for various
hydrated and dehydrated ionic forms.3 The greatest distortions arise among the
dehydrated forms. The more strongly an oxygen atom is bonded to an ex-
changeable cation the greater the T-0 bond length., Hydrated forms have more
uniform bond lengths and bond angles. The T-0-T angles fall mainly in the
range 13&-155” with the hydrated forms showing a smaller spread. Ion
exchange is found to have quite profound effects on various cation-oxygen and
oxygen-oxygen bond lengths. The key effect of cation exchange is to induce
distortions in the hexagonal prisms which in turn twist the bridging 4-rings
(rings composed of 4 oxygens). Distortions of the 4-rings of the hexagonal
prisms and the 6-rings separating sodalite and supercage cavities are not so
pronounced. Occupancy of site I by small di- and tri-valent cations seems to
increase the free diameter of this latter 6-ring at the expense of the free diameter
of the 6-rings in the hexagonal prisms.
The nomenclature used for the various cation sites now seems to have been
adopted by most workers in this field. Site I is situated at the centre of the
hexagonal prism, I’ on a triad axis, displaced into the sodalite cage from the
hexagonal face shared by sodalite cage and hexagonal prism, 11’ on a triad axis
but displaced into the sodalite cage from the unshared 6-ring between sodalite
cage and supercage, I1 slightly, and 11* considerably, displaced from this un-
shared 6-ring into the supercage, I11 displaced into supercage from bridging
4-rings, V displaced slightly from centre of the 12-ring separating supercages
(Figures 1 and 2, in reference 3 , show the basic sodalite building unit and the
position of most of these sites).

Si,Al Order-Disorder--Synthetic zeolites are grown under conditions which

favour Si,Al d i ~ o r d e r .Olson‘
~ established that hydrated Na-X has Fd3 sym-
metry and not Fd3m of the ideal faujasite framework. The mean T-0 distances
of the SiO, and A10, tetrahedra are 0.1619 and 0.1729nm respectively. The
latest compilation7 of T-0 distances suggests reference values of 0.1605 and
0.1757 nm respectively for these bond lengths. Olson’s data suggest occupancies,
therefore, of 0.91 Si, 0.09 A1 and 0.18 Si, 0-82A1 in the tetrahedra. The cell

’ W. M. Meier, ‘Molecular Sieves’, Society of Chemical Industry, London, 1968, p. 10.

W. M . Meier and D. H. Olson, ‘Molecular Sieve Zeolites’, 2nd Internat. Conf. Amer.
Chem. SOC.,Worcester, U.S.A., 1970.
J . V. Smith, ‘Molecular Sieve Zeolites’, 2nd Internat. Conf. Amer. Chem. SOC.,
Worcester, U.S.A., 1970.
* D. H . Olson and E. Dempsey, J . Catalysis, 1969, 13, 221.
T. F. W. Barth, ‘Feldspars’, Wiley, New York, 1969.
D. H . Olson, J . Phys. Chem., 1970, 74, 2758.
P. H . Ribbe and G. V. Gibbs, Amer. Mineralogist, 1969, 54, 85.
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Ion E,whange in Zeolites 193

content of his Na-X of 88 A1 and 104 Si atoms prohibits complete Fd3 order, but
strong long-range order is indicated.
Several authors have discussed order-disorder in these structures. Dempsey
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et al.,8*9assuming identical building units having zero net charge and dipole
moment, obtained ordered structures when the A1 contents were 96, 88, 80, 72,
64, 56, 48 etc. in a unit cell which contained 192 T atoms. They measured the
unit cell dimensions of 21 specimens containing A1 contents in the range 49-96
per unit cell and found discontinuities at specdic A1 contents which were inter-
preted as rearrangement of T atoms in accord with the theoretical analysis.
Smith3showed that the spread of unit cell dimensions quoted by various groups
at specific Si : A1 ratios was much larger than the size of these discontinuities. It is
difficult to eliminate non-structural A1 impurity in the chemical analysis of these
materials, and this may be the explanation of the differences and possibly of the
discontinuities. Natural faujasite, which was presumably formed much more
slowly than synthetic materials, seems to be more ordered than these synthetic
samples.
Infrared absorption and nuclear quadrupole resonance techniques can be
used to evaluate Si-A1 orderaisorder in aluminosilicates. Mossbauer
spectroscopy should also be capable of giving information about the symmetry
of the electric fields at cation sites.
Framework Hydroxy-groups-Framework hydroxy-groups are important as
they are centres for Brmsted and Lewis acid sites which seem to act as points of
catalytic activity. The nature and location of framework hydroxy-groups have
been reviewed by Ward''-l3 and Yates.14 H-forms of these zeolites, which
are formed by heating NHf -exchanged samples, give the clearest results. Olson
and Dempsey4 determined the structure of dehydrated H-faujasite. Most of
the protons in this material seem to be attached to two different types of oxygens
which form the hexagonal prisms. One O H group has a stretching wavenumber of
3550 cm- and is nor perturbed by sorbates which cannot pass into the sodalite
unit ; and hence it must be directed into the hexagonal prism, while the other has a
frequency of 3650 cm-I and since it is perturbed by large sorbate molecules is
presumably directed into the supercage.
X-Ray methods are too insensitive to establish the location of framework OH
groups in zeolites containing cations, but the presence of 3550 and 3650 cm-
stretching bands in the i.r. suggests that protons are attached to the same oxygens
as in the H-forms. However, i.r. measurements may be too insensitive to pick
up the small differences in stretching frequencies of differently sited OH groups.

* E. Dempsey, 'Molecular Sieves', Society of Chemical Industry, London, 1968, p. 293.

E. Dempsey, G . H . Kuhl, and D. H . Olson, J . Phys. Chem., 1969,73, 387.
lo F. Laves and S. Hafner, Norsk. Geol. Tidsskr., 1962, 42, 57.
I' J. W. Ward, 'Molecular Sieve Zeolites', 2nd Internat. Conf. Amer. Chern. SOC.,
Worcester, U.S.A., 1970.
J . W. Ward, J . Phys. Chem., 1969,73, 2086.
l 3 J. W. Ward and R . C. Hansford, J . Catalysis, 1969, 13, 364.
l4 D . J. C. Yates, Catalysis Reu., 1968, 2, 113.
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194 L . V . C. Rees
Detailed interpretation of hydroxy-group locations in cation-bearing zeolites is
given in various paper^.^*'^*'^-'^
Removal of Oxygen from Framework.-When NH4-Y is heated, dehydrated
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H-Y is formed and on further heating 2 hydroxy-groups from the framework

condense to form water and leave an oxide ion and an oxygen vacancy in the
framework.16*’ Kerr and c o - w ~ r k e r s ’ ~have
~ ~ ~shown
- ~ ~ that these reac-
tions are complex and the production of a form thermally stable above 1000 “C
depends critically on the method of deammoniation and dehydration. In the
production of this stable material 25% of the framework A1 is converted into
exchangeable A1 in the form of Al(OH)2f.I8Maher and his associates24 confirm
that ‘decationated’ Y or, as they prefer to call it, Sodium-Aluminium-Y
[(Na/Al)-V contains aluminium derived from framework Al. ,The ‘ultra-stable’
form of McDaniel and Maher” was produced by further treatment of the
(Na/Al)-Y with ammonium sulphate solutions and then calcination at 870 “ C .
This ‘ultra-stable’ Y shows the loss of the 15 A1 atoms per unit cell present in
(Na/Al)-Y as exchangeable cation, but this A1 remains in the structure as an
insoluble, polymeric alumina compound.
KerrZ5reduced the A1 framework content from 50 to 32.8 per unit cell by
extraction with the acid form of edta. This Al-deficient material also showed
increased thermal stability.
Cationic Forms of X, Y, and Faujasite.-Dehydrated Samples. Water forms
hydration complexes with the exchangeable cations and interacts electrostatically
with the framework oxygens. The hydration complexes with monovalent
cations are weak and dehydration is relatively easy. The hgher the valency of
the cation the stronger is the hydration complex, and with certain polyvalent
cations polarisation energy becomes strong enough to break the water molecule
into a hydroxy-group, which bonds to the cation, and a proton, which becomes
attached to a framework oxygen.
Certain cation forms of these zeolites have specific catalytic properties. In
order to elucidate the mechanism of catalysis it is important to know the site
positions occupied by the cations in these exchanged forms. Much work has
been done to ascertain these cation positions and the present state of knowledge is
summarised in Table 1. These results have been deduced from X-ray diffraction
l5 E. Dempsey and D . H. Olson, J . Catalysis, 1969, 15, 309.
l6 J. B. Utterhoeven, R . Schoonheydt, B. V. Liengme, and W. K. Hall, J . Catalysis, 1969,
13, 425.
’’ J. W. Ward and R. C. Hansford, J . Caralysis, 1969, 15, 31 1.
la G . T . Kerr.J. Phys. Chern., 1967, 71, 4155.
l9 C. V. McDaniel and P. K . Maher, ‘Molecular Sieves’, Society of Chemical Industry,
London, 1968, p. 186.
L o G . T. Kerr, J . Catalysis, 1969, 15, 200.
2 1 G. T. Kerr. .I. Phys. Chern., 1969, ?3, 2780.
* * G. T. Kerr, J . Cattanach, and E. L. Wu, J . Catalysis, 1969.13. 114.
G. T. Kerr and G. F. Shipman, J . Phys. Chern., 1968, 72, 3071.
2 4 P. K. Maher, F. D. Hunter, and J. Scherzer, ‘Molecular Sieve Zeolites’, 2nd Internat.
Conf. Amer. Chem. SOC., Worcester, U.S.A., 1970.
2 5 G . T. Kerr, J . Phys. Chern., 1968,72, 2594.
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Ion Exchange in Zeolites

Table 1 Cation Positions in X, Y, and Fuujusite
Site Occupancy per Unit Cell
I I' 11' I1 11*
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Maximum Available 16 32 32 32 32
Strongly Dehydrated
Na-Y" 7.8 20.2 - 31.2 -

K-Yo 12.0 14.6 - 31.0 -

Ag-Y" 16.0 11.0 - 29.2 -
K-faujasiteb 8-6 12-9 - 31.7 -
Ba-faujasiteb 7.3 5.0 - 11.3 -
Ca-faujasi te' 14.2 2.6 - 11-4 -

Ni-fauj asited 10-6 3.2 1.9 6.4 -

La-faujasite' 11.8 2.5 - 1.5 -
La-faujasite' at 420 "C 11.7 2.5 - 1-4 -

Partially Dehydrated
Na,Ce-faujasitef 3.4 Na 11.5 Ce 16 H 2 0 10.7 Na -
La-Yg at 725 " C 5.2 8.9 - 5.5 -
La-Xf - 30.0 32H2O - -
Ca-Xh*' 7-5
17.3 {li::H20
17.3 -
Sr-Xh*'outgassed at 400 " C 11.2

Sr-Xh*'outgassed at 680 "C

7-0
{ z:42H,019-5 -

La-Xj at 425 " C

6.1

5.0
12-0

15.2
{ 4:; H 2 020.3
- 4.9
-

-
La-Xj at 735 " C 5.2 14.1 - 6.3 -

Hydrated
Faujasitek - 16.0 32HzO - 11HZO -
(Na, Ca)
Ca-faujasite' - 9.7 11.5 - 23 H2O 2.2
La-faujasite"' -
3.3 28H2O - I4H2O 10.3
(Ce,Na,Ca)-faujasiteI - 18.0Na 32H,O - 2 6 H 2 0 5.8Ce
Na-X"

(Sr42Na)-X"
9.0
{1x20
2-1 Sr 11.1 Sr
26H20E;20
32H20 15.0Sr
-
-
-

(Sr,,Na,,)-X" 12.0Na 7.3 Sr 26 H,O 11.5 Sr - -

La-Xf - 12.0 32 H2O 17.0 - 4.0
La-Xf 5-0 13.8 24 H2O 13.2 - 3.4
G. R. Eulenberger, J. G. Keil, and D. P. Shoemaker. J. Phys. Chem., 1967, 71, 1812.
J. Pluth and V. Shomaker, unpublished data.
J . M. Bennett and J. V. Smith, Materials Res. Bull., 1968, 3, 633.
D. H. Olson, J. Phys. Chem., 1968, 72,4366.
' J. M. Bennett and J. V. Smith, Materials Res. Bull., 1968, 3, 865; 1969, 4, 7.
f D. H. Olson, G. T. Kokotailo, and J. F. Charnell, J . Colloidlnterface Sci.. 1968.28.305.

* J. V. Smith, J. M. Bennett, and E. M. Flanigen, Nature, 1967, 215, 241.

D. H. Olson and E. Dempsey, J. Catalysis, 1969, 13, 221.
D. H. Olson, J. Phys. Chem., 1968,72, 1400.
j J. M. Bennett, J. V. Smith, and C. L. Angell, Materials Res. Bull., 1969, 4, 77.
' W. H. Baur, Amer. Mineralogist, 1964, 49, 697.
' J. M. Bennett and J. V. Smith, Materials Res. Bull., 1968, 3, 933.
J. M. Bennett and J. V. Smith, Materials Res. Bull., 1969, 4, 343.
" D. H. Olson, J. Phys. Chem., 1970,74,2758.
' D. H. Olson and H. S. Sherry, J. Phys. Chem., 1968. 72, 4095.
 View Article Online

196 L. V . C. Rees
studies, and a certain element of subjectiveness is necessary to arrive at these
distributions. They should, therefore, be treated with some circumspection.
In zeolite Y the negative charge on the framework is ca. 56-60 units while
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in the zeolite X, which is more aluminous, there are 8&88 units of charge
per unit cell. Dempsey26 has made some important theoretical calculations of
‘Madelung’ constants (or reduced ionic potentials) for cations of various size,
valency, and occupancy among available sites. Although the model used is
somewhat idealised, good agreement between calculated and experimental
distributions of monovalent cations among the available sites was found.
The agreement was not so good for divalent and trivalent cations and it was
postulated that the discrepancies were due to residual water in the crystals used
in the X-rays studies which made site I’ more favourable than site I, the site which
according to calculations should be the preferred site for polyvalent ions of
radius less than 0.13 nm. Site I is the only site which allows a cation to be en-
closed by framework oxygens and is thus the preferred site unless size or cation-
sorbate attraction produces a lower free energy at another site. However, the
number of type I sites is limited (see Table 1). When cations occupy adjacent I
and I’ sites electrostatic repulsion makes this situation an unfavoured one.
This sharing problem is even more severe with I1 and 11’ sites. Electrostatically,
the best way to distribute 58 monovalent cations in zeolite Y is to have 32 in 11,
6 in I, and 20 in 1’. This distribution can be accomplished without I and I’
cations being adjacent to each other.
The K-faujasite single crystal data agree with this distribution but the powder
data for Na-, K-, and Ag-Y do not. The deviation for Na-Y is within the experi-
mental error and this may be the explanation for the K-Y discrepancy. The
Ag-Y results suggest, however, that enhanced site I occupation is produced by a
stronger tendency for covalent bonding between Ag and site I oxygens. There are
considerable problems in placing the 86 cations per unit cell whch are usually
present in zeolite X. At present no data have been published giving the location of
monovalent cations in dehydrated X.
In Y and faujasite the 29 divalent cations present in divalent cation forms can
be entirely accommodated in I and I1 sites. The distribution of Ca2+ ions in
dehydrated Ca-faujasite (see Table 1) is 14.2 in I, 2.6 in 1‘, and 11.4 in 11. The
type I and I’ calcium ions can be placed in non-adjacent sites. Dempsey and
Olson2’ suggest that partial hydration makes the I’ site energetically more favour-
able such that n(1) + 0.5n(I’) = 16.
Table 1 shows that site I is the preferred site for La3 ions in strongly dehy-
+

drated La-faujasite. The few La3+ ions in I’ and I1 sites may be due to residual
water and/or high A1 content of a few 6-rings.
When these zeolites are only partially dehydrated the strong polyvalent cation-
residual water bonding makes site I’ preferred to I. Although site I’ has framework
oxygens co-ordinated to the cation on one side only, this deficiency is overcome

26 E. Dempsey, J . Phys. Chem., 1969,73, 3660.

27 E. Dempsey and D. H. Olson, J . Phys. Chem., 1970.74, 305.
 View Article Online

Ion Exchange in Zeolites 197

by water molecules occupying either 11’ sites or the site in the middle of the
sodalite cage (see ref. g , Table 1).
It has been suggested3 that a water molecule can bridge 2 or more La ions in I’
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sites. Hence fully exchanged La-Y, containing 19 La3+ions, needs only 10 water
molecules at most compared with the 260 present in the fully hydrated material.
Since the feed materials used by the petroleum industry contain traces of water, it
is reasonable to assume that in those active catalytic zeolites containing polyvalent
cations these cations will be occupying sites in the sodalite cage rather than I sites.
Hydrated Samples. The data in Table 1 for hydrated materials are unsatisfactory
since the positions of all the cations and water molecules have not been established.
Ion-exchange with Na-X and Na-Y will be described in more detail
in a later section, but these showed that only a limited number of Na ions could
be replaced when exchange at room temperature involved an ion too large to pass
through a 6-ring. The cut-offs in the exchange isotherms clearly indicated in the
case of Y that 16 Na ions were contained in the sodalite cage and/or hexagonal
prism sites. With X no such clear-cut conclusion could be drawn. It appeared
with X that the number of Na ions contained in 11’, I’ and I sites was dependent
on the character of the counter-ion and possibly on the degree of exchange.
When polyvalent ions are present in hydrated Y or faujasite the data in Table 1
suggest that the lowest free energy is obtained when the polyvalent ions occupy
mainly supercage sites with Na ions in sodalite and hexagonal prism sites. The
polyvalent ions presumably prefer supercage sites so as to be co-ordinated to the
maximum possible number of water molecules and thus minimize the energy
required to be supplied to reduce the size of the hydration shell whch exists in
the solution phase in order to allow them to pass into the large channels of the
zeolite. With zeolite X, because of the higher density of cation, coulombic
repulsions will force ions into unoccupied 11’, 1’, and I sites to achieve a state of
lowest free energy. In these hydrated materials cations have been found com-
pletely surrounded by water molecules in a new site (site V) near the centre of the
12-ring in the supercage (see Table 1).
A most comprehensive study of cation and water molecule positions in hydrated
Na-X has recently been made.6 Table 1 shows that Na ions occupy I, 1’, and I1
sites with water molecules established in 1’, 11’, and I1 sites. Seven sites in the
supercage were also occupied at low levels. Olson suggested that in hydrated
systems cations occupy site I1 only when this site has 3 A1 in the 6-ring and thus
provides a favourable electrostatic environment. Since faujasite and Y have less
than 2 A1 on average in a 6-ring these zeolites should have few cations in I1 sites.
This suggestion seems to be consistent with available experimental results.
La3 ions in La-X are shown in Table 1 to occupy I’ and I1 sites predominantly,
+

with a small number in V sites. Site 11’ is occupied by water molecules which
R. M. Barrer, L. V. C. Rees, and M . Shamsuzzoha, J . Inorg. Nuclear Chem., 1966, 28,
629.
29 R. M. Barrer, J . A. Davies, and L. V. C. Rees, J . Inorg. Nuclear Chem., 1968,30, 3 3 3 3 .
30 R. M. Barrer, J. A. Davies, and L. V. C. Rees, J . Inorg. Nuclear Chem., 1969, 31, 2599.
31 H. S. Sherry, J . Phys. Chem., 1966, 70, 1158.
’‘ H. S. Sherry, J . Phys. Chem., 1968, 7 2 , 4086.
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198 L. V . C . Rees
bond strongly with the I’ and I1 La3+ ions. The higher A1 content of the 6-rings
must favour occupancy of sites I’ and I1 at the expense of site V, a site more
favouried by faujasite and Y zeolite. I’ and I1 are the favoured sites for Sr2+
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occupation according to Olson and Sherry.33

Other Zeolites.-Breck, in his introduction to the Second Zeolite Conference,
listed the structures which have recently been e l ~ c i d a t e d .Synthetic
~~ zeolites
which should have interesting catalytic and other properties and which have
been recently synthesised are zeolites L,35 and T.37 Comprehensive ion-
exchange studies38 have been made with zeolite T in the Mobil laboratories,
presumably as a complement to catalytic studies. These three zeolites have been
shown by Barrer and Villiger3’ to be constructed with a similar building unit
to that found in offretite and erionite. These natural minerals have similar
structures and were thought originally to be identical. However, Bennett and
Gard3’ found that the ‘c’ spacing in offretite was half that in erionite. Gard
and Tait4’ have analysed various synthetic zeolite T samples and shown that
these samples had the same structure as offretite. They showed that this zeolite T
has channels of 0.63 nm free diameter and should be capable of sorbing much
larger molecules or cations than erionite, but a small degree of stacking disorder
would constrict the channels with windows identical to those which exist in
erionite. The K + ion was placed in each cancrinite cage and the remaining cations
partially occupied two different sets of sites located on the axes parallel to c of
the single 6-rings and the large channels. The cations on these latter sites are
readily accessible to ion exchange if no or few stacking faults exist but the K +
ions in the cancrinite cages are not exchangeable below 300°C.38
Barrer and Villiger,35in determining the structure of zeolite L, describe the
difficultiesencountered in the elucidation of zeolite structures from X-ray powder
data. They postulated that the structure is based on polyhedral cages which are
formed by five 6-rings and six 4-rings as are found in cancrinite, erionite, and
offretite. In this structure columns of hexagonal prisms and polyhedra running
parallel to the ‘c’ axis alternate. The structure contains 12-rings which circum-
scribe wide channels which also run parallel to the ‘c’ axis. These 12-rings have
free diameters of 0.71-0.78 nm. Four cation positions were found. Three of
these (A, B, and C) are outside the main channels and are closely surrounded by
framework oxygens. The fourth site (D) is in the widest part of the main channel
close to the channel wall. Site A, which is probably occupied only by K + ions
in a (Na,K)-L, is in the middle of the hexagonal prism. Site B is in the centre of
33 D. H. Olson and H. S. Sherry, J . Phys. Chem., 1968, 72, 4095.
34 D. W. Breck, ‘Molecular Sieve Zeolites’, 2nd Internat. Conf. Amer. Chem. SOC.,
Worcester, U.S.A., 1970.
35 R. M. Barrer and H. Villiger, 2. Krist., 1969, 128, 352.
’* R. M. Barrer and H. Villiger, Chem. Comm., 1969, 659.
37 D. W. Breck and W. A. Acara, U.S.P.2,950,952, (1960).
38 H. S. Sherry, ‘Ion Exchange in the Process Industries’, Society of Chemical Industry,
London, 1970, p. 329.
j 9 J. M. Bennett and J. A. Gard, Nature, 1967, 214, 1005.
40 J. A . Gard and J. M. Tait, ‘Molecular Sieve Zeolites’, 2nd Internat. Conf. Amer. Chem.
SOC.,Worcester, U.S.A., 1970.
 View Article Online

Ion Exchange in Zeolites 199

the cancrinite cavity and is fully occupied by K '. Site C contains K + and is
located midway between the centres of two adjacent cancrinite cavities. Access to
these sites from the large channel is through an 8-ring with a free diameter of
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0.15 nm. Site D is partially occupied by Na' in the (Na,K)-form and by K +

in the K-form. The cations on this site are the only ones available for exchange
at room temperature.
Zeolites L, offretite, and erionite have marked tendencies to co-~rystallise,~
which suggests that common structural elements are involved in their alumino-
silicate frameworks and confirms the structure proposed by Barrer and Villiger
for zeolite L. It was also found that X-ray diffraction methods can now differen-
tiate between offretite and erionite structures. By means of X-ray diffraction and
electron microscopy the positions of the cations in various cation forms of
unfaulted offretite were determined.42 The molecular sieve properties of these
cationic forms of offretite agreed with these cation positions. It was found that
the sorption properties were regulated by the size of the cation in the main channel.
Structures have been proposed by Barrer and Villiger35 for a considerable
number of, so far, undiscovered zeolites with structures similar to zeolite L.
All of these structures can be allocated to the chabazite family. Some of these
zeolites, if capable of synthesis, would have very large intracrystalline pores and
large total porosities (-0.6 of the crystal volume would be free volume). The
main channels in these structureswould contain 18-ringwindows.
Although some doubt was expressed about the validity of certain experimental
results, exceedingly interesting new zeolites were announced at the Second
Zeolite Conference by Flanigen and G r ~ s e . ~They , prepared zeolites in which
[PO,] replaced [SiO,] tetrahedra. Since phosphorus is pentavalent while silicon
is tetravalent, excess positive charge is built into the structure. Phosphorus was
reported to have been incorporated into analcime, phillipsite, chabazite, and
zeolites A, L, and P. Since aluminium was found to be a necessary ingredient of
the starting gel and since the resulting zeolites all contained excess aluminium
over phosphorus, these zeolites contained cations to balance the excess negative
charge. We still await, therefore, a zeolitic anion-exchanger.
Rees and Berry,44 by studying the sorption properties of zeolite A as the degree
of Na' replacement by Ca2+ increased, showed that Ca2+ ions preferred the
6-ring sites to the 8-ring sites in this structure after dehydration and also when
partially solvated by NH,. Using a similar technique Egerton and Stone45
followed the amount of CO sorbed and the heat of sorption as Na' replaced
Ca2' in zeolite Y . Little change occurred in these quantities until 50% of the
Na+ ions had been replaced. They concluded that the first 16 Ca2' ions per unit
41
1. S. Kerr, J. A . Good, R . M. Barrer, and I. M. Galabova, Amer. Mineralogist, 1970,
55, 441.
4 2 R . Aiello, R . M . Barrer, J. A. Davies, and I. S. Kerr, Trans. Faraduy SOC.,1970, 66,
1610.
4 3 E. M. Flanigen and R. W. Grose, 'Molecular Sieve Zeolites', 2nd Internat. Conf.
Amer. Chem. SOC., Worcester, U.S.A., 1970.
4 4 L. V. C. Rees and T. Berry, 'Molecular Sieves', Society of Chemical Industry, London,
1968, p. 149.
" T. A. Egerton and F. A. Stone, Trans. Faraday Soc., 1970, 66, 2364.
 View Article Online

200 L. V . C . Rees
cell introduced by exchange from aqueous solutions occupy I, 1', or 11' sites on
subsequent dehydration. Further exchange forces Ca2+ ions to occupy I1 sites,
where they are now exposed to the CO sorbate molecules. The amount sorbed
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and the heat of sorption increase greatly as the number of Ca2+ ions in I1 sites
increase.
The kinetics of n-alkane adsorption on zeolite A exchanged with Mg2',
Ca2', and Sr2+ have been studied.46 The adsorption of water by t h s same
zeolite containing Na', Mg2+,Ca2+, Sr2+,and Ba" has been followed as a
function of degree of exchange and temperature of thermal ~ r e - t r e a t m e n t . ~ ~
(Na,Ba)-A, containing more than 55 % Ba, showed a rapid decrease in the sorp-
tion capacity, confirming previous reports of the lack of thermal stability of the A
lattice when in the Ba2+ form. The adsorption of water has also been used to
ascertain the effect of ion exchange in zeolites A and X.48949 The locations of
Na+, K', and Li' ions in zeolites A and B have been postulated from water and
n-hexane adsorption isotherm^.^' At small degrees of exchange of Na+ by
Li', the Li' ions occupy the 8-ring site in A and the 6-ring site in B. K + ions
occupy the 8-ring sites in both A and B on initial replacement of Li+ but sit in
the 8-ring sites in A and 6-ring sites in B on initial replacement of Na'. From
the isosteric heat of sorption of NH, in (Na,Mg)-A it was concluded51 that
NH, is sorbed initially on Mg2+in 6-ring sites, then on Na' at 4-ring sites, and
finally in the 8-ring windows. In a similar way the position of M, where M = Cu,
Mn, Ni, and Co, in (Na,M)-X was determined.52 The adsorption of gases at
low pressures on zeolite X was modified by ion exchange. Both the kinetics
of adsorption and the equilibrium pressures were influenced by the cation present
in the channels5,
The chromatographic separations of various gases were found to be dependent
on the type of cation and degree of exchange in zeolite X.54Similarly, heats of
sorption and specific retention volumes were used to estimate the location of
rare-earth ions and the effect of temperature on their movements in f a ~ j a s i t e . ~ ~
Heats of immersion of Na-Y, (Na,Ca)-Y, and Ca-Y in various organic liquids
indicated a five-fold increase in the electric field strengths on going from
Na-Y -+ Ca-Y. The field strengths start to increase when 40% of the Na ' ions
are replaced by CaZ . 5 6 Heats of immersion in water have been determined for a
+

number of outgassed porous crystals enriched in various cations by ion exchange.

4b P. N . Galich, D. I. Evseeva, and G. P. Lugovskaya, Dopouidi. Akad. Nauk Ukrain.
R . S . R . Ser. B , 1969, 31, 897.
47 M . Mange, J. L. Thomas, and C. Eyraud, Bull. Soc. chim. France, 1969, 10, 3 3 7 5 .
48 I. E. Neimark, Izvest. Otdel. Khim. Nauk, Bulg. Akad. Nauk, 1968, 1, 31.
49 D. Kunath, H . J . Spangenberg, H . Stach, and W. Schirmer, Z . Chem., 1970, 10, 1 .
P. Collin and R. Wey, Compt. rend., 1970, 270, D , 1069.
H . Stach, T. Peinze, K. Fielder, and W. Schirmer, Z . Chem., 1970, 10, 229.
H . Stach. H . Luther, and W. Schirmer, Z. Chem., 1970, 10, 228.
53 V. Bosacek, J . Krasa, and P. J . Schurer, Czech. J . Phys., 1970, 20, 912.
54 T. G . Andronikashvili, G . V. Tsitsishvili, and Sh. D. Sabelashvili, Saobshch. Akad.
Nauk Gruz. S.S.R., 1969, 56, 113.
55 Kh. M. Minzchev, N. V. Mirzabekova. V. I. Bogomolov, and Ya. I. Isakov. Izr*esr.
Akad. Nauk S . S . S . R . , Ser. khim., 1969. 2346.
" K. Tsutsumi and H . Takahashi, J . Phys. Chem., 1970.74, 2710.
 View Article Online

Ion Exchange in Zeolites 20 1

From the influence of ion exchange upon these integral heats, insight into cation
positions could be d e r i ~ e d . ~ '
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3 Ion Exchange in Zeolites

Zeolites have an important part to play in the development of the theory of ion-
exchange reactions. They are crystalline materials which can be readily syn-
thesised with reproducible properties. As shown in Section 2, the structures and
positions of cations and water molecules can now be established in many cases.
These factors are essential requirements of exchange materials used in the develop-
ment of a comprehensive theory of ion exchange.

Equilibrium Studies.-Zeolites X and Y. Ion-exchange equilibria have been

thoroughly studied in these zeolites by Barrer and his associate^^*^^^ and by
S h e r r ~ . From
~ ~ , ~these
~ exchange isotherms the standard free energy of ex-
change AG*was determined. Sherry measured AG*at two or three temperatures
to obtain standard enthalpies A P and entropies A F for several pairs of ions.
Barrer et al. employed a simple isothermal calorimeter to obtain A P at 25 "C.
In the course of these measurements they also obtained partial heats of exchange
AHxe and differential heats dHxO/dx where x is the degree of exchange. AH* was
found to fall within the range 0- 12 kJ (8. equiv. of exchange)- '. Because of the
low values found for AiH*the calorimetrically derived values are more reliable.
However, AHx*could not be determined calorimetrically when equilibrium was
established slowly. The similarity of the signs and the magnitudes of AHOfor
corresponding exchanges in zeolites X and Y indicates similar binding energies
of the solvated cations in each zeolite. The heats in X are consistently more
endothermal than the corresponding values in Y. In some exchanges in zeolite X
involving uni-univalent ions there is pronounced change in the curve of aAHxO/ax
us. x at a cationic composition of about x = 0.6, indicating at least two kinds
of sites in X. No such pronounced change was observed with Y. In the case of
uni-divalent exchange these curves differ considerably for X and. Y. It was
concluded that out of the 36 Na' ions that are considered as exchangeable in Y ,
just over one half behave differently from the remainder.
The. entropies AS*for replacement of Na+ by K + , Rb', and Cs+ are negative
in both X and Y zeolites and positive for replacement by Ca2+ in Y. Entropy
changes are in part associated with changes of hydration of the ions as they leave
the aqueous solution and enter the zeolite media, and vice versa. The restricted
nature of the intracrystalline environment may impose large changes in the
hydration state of ions when they enter the zeolite channel. The negative values
for ASefound with the uni-univalent exchanges are in part due to an overall
increase in the hydration as the Na' ions replace the larger counter-ion in the
solution phase. The positive value for AS0 in the case of Ca2+ represents in
part a decrease in hydration of the solution phase and an increased configurational
entropy due to one Ca2 ion replacing two Na' ions in the zeolite.
+

ST R . M . Barrer and P. J . Cram, 'Molecular Sieve Zeolites', 2nd Internat. Conf. Amer.
Chem. SOC.,Worcester, U.S.A., 1970.
 View Article Online

202 L. V . C. Rees
With Na-Y, both Barrer et and Sherry 32 found that 16 Na+ ions per unit
cell could not be replaced by Rb' and Cs+ at 25 "C. These results suggest that
the 16 Na' ions known from X-ray studies to be contained in I and I' sites cannot
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be replaced by Cs' and Rb'. The 6-ring controlling access to these sites has a
free diameter of 0.25 nm and Cs' and Rb' cannot overcome this energy barrier
at a measureable rate at 25 "C. Sherry, in similar experiments with zeolite X,31
assumed that 16 Na' ions were irreplaceable by Rb' and Cs' and extrapolated
his exchange isotherms to 82% exchange of Na+ when the solution phase con-
tained only Rb+ or Cs' ions. Barrer, Rees, and Shamsuzzoha" found that
exchange ceased at 65% replacement of Na', a figure which was confirmed by
Theng et uI.~'and is now accepted by Sherry59after further work. In zeolite X,
therefore, 32 of the 86 Na' ions per unit cell cannot be replaced. It was suggested3'
that when ions as large as Rb' and Cs+ have to be accommodated in the super-
cages coulombic repulsions force Na+ ions to move from the supercage into less
favourable I' and 11' sites. However, one could argue that exchange should
proceed to a higher limit for Rb+ than Cs' since Rb' is smaller than Cs+.
Alkali-metal ion exchange in isostructural zeolites X and Y can be used to
ascertain the effect of change of concentration of framework charge on selectivi-
ties and standard free energies. At low loadings of the ingoing ion the selectivity
series for both Na-X and Na-Y is Cs > Rb > K > Na > Li. At 50% exchange,
the selectivity series in zeolite X is Na > K > Rb > Cs > Li, and in zeolite Y is
Cs > Rb > K > Na > Li. These selectivities are approximately representative
of the free energy changes involved in these reactions. The changes in selectivities
on going from Y to X zeolite represent the net effect of increased density of cation
and thus a decrease in the number of water molecules per ion and changes in the
coulombic energy term on going from a less highly to a more highly charged
surface in the zeolite. In these zeolites there are 32 I1 sites to accommodate
34-36 ions in Y and 69-70 ions in X. Sherry has concluded that, since the
above selectivity series does not change on going from low loadings to 50%
exchange in zeolite Y, ions do not occupy I1 sites in hydrated Y, while in X this
change in the selectivity series indicates that some of the cations are forced to
take up I1 sites. However, Barrer, Davies, and R e e found ~ ~ ~that the Na -B K
exchange isotherm in zeolite Y was little changed on replacing the water in the
channels by methanol, but the very slow kinetics of exchange in methanol
indicated that the cations were strongly associated with the lattice sites when a
solvent of low dielectric constant filled the channels.
One very interesting difference in the exchange behaviour of X and Y is shown
in the exchange of Na+ by Tl'. At 25 "C a 100% exchange of Na' can be
accomplished with X, but the 16 Na' ions in the small cages of Y cannot be re-
~ * ~ ' assumed, since the 6-rings of Y are 0.001 nm smaller in
p l a ~ e d . ' * * ~ Sherry
free diameter than those in X, that this was a kinetic effect. However, Smith3
has commented on the ease by which framework oxygens relax to accommodate
58 B. K . Theng, E. Vansant, and J . B. Uytterhoeven, Trans. Faraduy SOC.,1968,64, 3370.
59 H. S. Sherry, 'Molecular Sieve Zeolites', 2nd Internat. Conf. Amer. Chem. SOC.,
Worcester, U.S.A., 1970.
 View Article Online

Ion Exchange in Zeolites 203

ions of differing size and it seems unlikely that this small difference in free dia-
meters of the respective 6-rings would reduce the rate of T1+ exchange in Y to
such an extent that no replacement of the 16 Na+ ions could be observed even
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after prolonged contact with T1+ solution. Barrer, Davies, and R e e assumed ~ ~ ~
that the higher framework charge of X enhances the polarisation energy with Ti+
sufficiently to change the free energy of the small cage sites from a positive
quantity in Y to a negative one in X. Sherry has d e m o n ~ t r a t e dfor
~ ~the readily
polarisable Ag' ion which completely replaces Na+ in both X and Y zeolites
that the isotherm with X shows a much greater specificity for Ag than the corres-
ponding isotherm with Y at all loadings. This indicates, firstly, that ion-frame-
work interactions are important in the supercage sites and, secondly, that these
interactions are greatly enhanced with the small cage sites in the more highly
charged X zeolite than with zeolite Y. Sherry59found that complete replacement
of Na' by T1+ occurred at 100°C and that the specificity of T1+ to Na' was
greater than one at all loadings. According to Sherry this confirmed his kinetic
interpretation of the partial sieving effect in Y, but he omits entropy of exchange
effects from his considerations.
The exchange of alkaline-earth ions in Na-X and Na-Y has been followed at
25 "C by Barrer and his associate^^^*^^ and over the temperature range 5-50 "C
by Sherry.3Z Both groups found with Ca2+ and Sr2+an initial fast exchange in
zeolite X followed by a slow one. At the end of the slow stage (approximately
4 days) complete replacement of N a + had been accomplished by both divalent
ions. These ions are highly hydrated and partial stripping of the solvation shell
is necessary to allow these ions to enter the small cages. The slow step is un-
doubtedly associated with this stripping reaction. The Na+-Ca2+ isotherm is
sigmoidal with a very high selectivity for Ca2+ initially, followed by a much
lower one when exchange involves small cage sites. In a very thorough ion-
exchange and X-ray study of Na+-Sr2+ exchange in X, Olson and Sherry33
found limited miscibility of the end members, as was found previously6' in other
zeolite exchanges. In the SrZ+-richphase, I sites are vacated by cation and this
loss of positive charge in the hexagonal prisms causes the oxygen atoms to move
apart, producing a sudden expansion of the unit cell at 71 % loading of Sr2+.
When Ba2+exchange in X was studied, Sherry found that 82% of the Na+ ions
could be replaced by Ba2 at 25 " C whereas Barrer, Rees, and Shamsuzzoha28
+

reported a cut-off in the exchange at 74%. This may be due to the presence of
some H 3 0 + ions in material used by these latter workers. Since Ba2+ and K +
have similar radii and K + exchanges rapidly into the small cages, the limited
exchange with Ba2+must be a result of the high energy of activation for diffusion
through the 6-ring between supercages and sodalite cages introduced by the
large hydration sheath around the Ba2 ion and unfavourable free-energy terms
+

when Ba2+ sits in these sites of limited free volume. Sherry 32 has shown that
increase in temperature loosens this hydration sheath and that complete exchange
can be accomplished at 50°C. From analysis of the sigmoidal isotherm Sherry

6o R. M . Barrer and L. Hinds, J . Chem. SOC.,1957, 1879.

 View Article Online

204 L. V . C. Rees
derived equilibrium constants for Ba2+ of 0.037 in the small cages and 72-5 for
the supercage sites.
In Na-Y both Sherry32and Barrer, Davies, and Rees'9 found that the 16 Na'
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ions in the small cages could not be replaced by Ca2+,Sr2+,or Ba2+ at 25°C.
Complete exchange still could not be accomplished by Sherry on elevating the
temperature. Barrer and his associates suggested that this limit to the exchange is
due to positive free energies for these divalent ions in the small cage sites. These
exchange systems are excellent examples, therefore, of how decrease in frame-
work charge can alter selectivities. The reduced interaction energy between
divalent cation and anionic framework site in zeolite Y makes AH*more positive
than for zeolite X and this is sufficient to change the sign of (AHe- 7 ' A S
for the small cage sites.
Rare-earth-exchanged forms of zeolites X and Y are very important catalysts
in the petroleum refining industry. Sherry6' has made a study of these systems.
At 25°C La3+ does not replace the 16 Naf ions per unit cell in the small cages
of zeolites X and Y. On raising the temperature to 100°C, 99% replacement of
Na' could be accomplished but only after 13 days of contact with the La3'
solution. Table 1 shows that some of these La3+ ions are sited in the small
cages. It is interesting to note that the high-temperature isotherm showing
complete exchange is not sigmoidal. Thus La3+ ions are preferred over Na+ ions
by the small cage sites even though a very high degree of stripping of the hydration
sheath is necessary before a La3 ion can enter the sodalite cage. This indicates
+

that the La3 ion-anionic framework interaction-energy is now sufficiently

+

large to make AG*for these sites negative whereas with the alkaline-earth ions
this energy term was still too small even in zeolite X to make AG*negative.
However, ASeshould be quite positive for this exchange and this may be the
dominating term in making AG*negative.
Theng, Vansant, and Uytterh~even~'studied the exchange of NH4+ and
alkylammonium ions in X and Y zeolites. They showed that 16 of the Na+ ions
per unit cell of Na-Y were not replaced by NH4+,which agreed with previous
With alkylammonium ions the maximum degree of exchange decreased
with increasing molecular weight of the counter-ion. The proportion of Na'
ions replaced was lower with X than with Y. The type of metal ion initially
present in the exchanger also affected the limit of exchange. They proposed that
as the length and the number of alkyl groups increased the electrostatic interaction
between cation and framework charge was reduced and the extent of exchange
decreased.
Other Zeolites. Barrer, Papadopoulos, and Rees62investigated alkylammonium
ion exchange in Na-clinoptilolite, a natural zeolitic mineral found in large quan-
tities in the U.S.A. They obtained isotherms at 60°C for NH,+, CH3NH3+,
(CH,),NH, , (CH 3)3NH+, C2H,NH , n-C3H,NH3 , i-C3H,NH, , and
+ + + +

'' H . S. Sherry, J . Colloid Interface Sci.,1968, 28, 288.

62 R. M . Barrer, R. Papadopoulos, and L. V. C. Rees, J. Inorg. Nuclear Chem., 1967,
29, 2047.
 View Article Online

Ion Exchange in Zeolites 205

n-C,H,NH,+ ions. Complete replacement of all the Na+ ions in this zeolite
(empirical formula Na,O.Al,O,. 10Si02.8.6H20)was accomplished by all the
above cations except (CH,),NH+, i-C3H7NH,+, and n-C,H,NH,+, for which
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only partial replacement was found. The water content of the exchanger decreased
with increased loading and with increased volume of the organic cation. This
decrease in water content introduces a large endothermic energy component into
the heat of exchange and this must have a significant effect on the size and sign of
Ace. Assuming that clinoptilolite is isostructural with heulandite, they concluded
that partial ion sieving is due to the existence of two networks of intersecting,
elliptical, channels which have different free diameters. Diffusion through one
channel system is controlled by 10-rings of free dimensions 0.79 nm by 0.35 nm
and through the other by 8-rings of free dimensions 0.44 nm by 0.30 nm. The ions
which show partial sieving effects could not enter the smaller channel network.
They also demonstrated that ions such as (CH,),N+ and t-C,H,NH3+, whose
smallest cross-sectional dimensions were much larger than 0.35 nm. were com-
pletely sieved whereas (CH,),NH ' and n-C,H,NH, + , with smallest cross-
sectional diameters of 0-42 and 0.40nm respectively, could enter the larger
channel. Barrer et al. concluded that these studies supported the proposal that
clinoptilolite was isostructural with heulandite.
Sherry has studied univalent and divalent ion exchange in zeolite T.38 This
material has the structure of offretite and is another example of a zeolite with two
networks of channels. One channel has an effective free diameter of 0.627 nm
and the other has two limiting apertures of 0.351 nm and 0.176 nm diameter. The
anhydrous unit cell content of the zeolite T used was K4[(A10,),(Si0,),,]. Ion
exchange with Li+, Na', N H 4 + ,Rb', Cs+, Ag', Ca2+,and Ba2+ replaces only
three K + ions per unit cell. The fourth K + ion, as supported by X-ray data, is
trapped in the smaller channel, presumably in the cancrinite cage. The thermo-
dynamic selectivity series is Cs+ > Rb+ > Ag+ > K + > NH4+ > Ba2+ >> Na'
> Ca2+ > Li'. Many monovalent cations are thus preferred to divalent ones.
Zeolite T has a denser framework containing fewer water molecules per unit
volume and a lower density of framework charge than zeolite Y. The results
found with zeolites X and Y would suggest that these properties of zeolite T should
tend to give preference to monovalent cations with little or no water of hydration.
Similar preference for monovalent cations was demonstrated by Barrer, Davies,
and Rees6, for ion exchange with Na-chabazite. Chabazite is a natural mineral
with a fairly high Si/Al ratio of 2.5 and a fairly compact channel structure. The
thermodynamic selectivity series found was
TI+ > K + > Ag+ > Rb' > NH,' > Pb" > Na' = Ba2+ > SrZ+ > Ca2+ > Li+
This series again demonstrates the preference by these types of structure for ions
with little or no hydration shell in the solution phase. The larger coulombic inter-
action between framework and divalent ion over the corresponding monovalent
ion interaction in this low charge density material is insufficient to overcome the

b3 R . M . Barrer, J . A . Davies, and L. V. C. Rees, J . Inorg. Nuclear Chem., 1969, 31, 219.
 View Article Online

206 L . V . C . Rees
large endothermic hydration term which arises when these divalent ions enter the
compact channel system. The high specificity of T1+ and Ag+ indicates that
interactions other than coulombic are important. The interesting preference of
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K + over Rb+ is presumably also evidence of the delicate balance of several factors
in the derivation of the final AG*value. An interesting kinetic effect was exhibited
by Ba2+. This ion exchanges extremely rapidly (almost as fast as the monovalent
ions) whereas Ca2 and SrZ exchange is quite slow. Heats of ion exchange were
+ +

measured calorimetrically by Barrer et a/. for these various ions in chabazite, and
complete thermodynamic data are given wherever possible.
Na+-Co2+ exchange in zeolite A has been measured at 25 "C by Radovanov
et The exchange was slow but reversible and the Co-A lattice was quite
stable. Ion exchange between variouszeolites and fused salts has been s t ~ d i e d . ~ ~ . ~ ~
L i q ~ o r n i kin
, ~a~similar study, measured the exchange of Na' in zeolite A with
various ions dissolved in molten NaNO, and of K + in the same zeolite with Li+,
Na', and Ag+ dissolved in molten KNO,. The selectivity series for Na!A was
Cs+ > T1+ > Ag+ > K+ > Li+ > Na+ and for K-A was Ag+ > Li+ > Na+
> K + . It is interesting to note that under these anhydrous conditions Lif is now
preferred to Na+ .
From the heats of ion exchange of hydrated zeolites with aqueous solutions of
ions, heats of immersion of dehydrated zeolites, and heats of hydration of gaseous
ions, Barrer and Davies6' calculated the heats of ion exchange between a gaseous
ion and a second ion in anhydrous zeolites X, Y, A, and chabazite. These heats
are large. When Na+ is replaced by K', Rb', and Cs', AH is endothermic and
in the range 5&120 kJ (g. equiv. of exchange)-'; when replaced by Li', AH is
exothermic and ca. - 100 kJ (g. equiv. of exchange)-'; and when replaced by
alkaline-earth ions AH is exothermic, being ca. - 360, - 280, and - 220 kJ (8.
equiv. of exchange)-' for Ca2+,SrZ+,and BaZ+respectively. The sign of these
heats is always opposite to that of the corresponding standard heat AHeof com-
plete exchange between aqueous solutions and hydrated crystals. The numerical
values of AH are normally in the sequence chabazite < zeolite A, X, and Y. The
large numerical magnitudes of AH reflect the very energetic nature of the 'solva-
tion' of cations by the anhydrous zeolite frameworks. The similarity of AH for a
given ion-pair in anhydrous zeolites X and Y is interesting in view of the difference
in framework charge and cation density. Exothermal electrostatic energy com-
ponents (ions with anionic oxygens) and endothermal components (ions with ions)
evidently add to about the same net value. In this same paper the heats of solva-
tion of individual gaseous ions with water, hydrated zeolite, and anhydrous zeolite
are compared. This first direct estimate of ion-bonding in anhydrous and hydrated
zeolites shows that the individual heats of solvation of a given ion in the hydrated
zeolite lie between those for solvation by anhydrous zeolite and water.
c* P. D . Radovanov, 0. M . Gacinovic, and I . J . Gal, J . Inorg. Nuclear Chem., 1969, 31,
298 1.
65 C. M . Callahan and M. A. Kay, J . Inorg. Nuclear Chem., 1966, 28, 233.
66 C. M . Callahan, J . Inorg. Nuclear Chem., 1966, 28, 2743.
67 M . Liquornik, Israel Atomic Energy Comm. IA [Rep] 1967, IA- 1124.
R. M . Barrer and J. A. Davies, J . Phys. and Chem. Solids, 1969, 30, 1921.
 View Article Online

Ion Exchange in Zeolites 207

Kinetics of Ion Exchange.-Tracer and Self-Diflusion. Rees and his associates
have made extensive studies of tracer diffusion and ion-exchange kinetics in several
zeoIi tes. 9-7 The tracer diffusion experiments indicated that channel aperture
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size, charge on framework and on diffusing ion, and concentration of zeolitic

water were important factors in controlling the rate.
Some extremely fine tracer diffusion measurements in zeolites A and X have
been made by Levi et al. Levi's group have developed two techniques for studying
the fast tracer exchanges encountered with these synthetic Using
these techniques Hoinkis and Levi reported that the exchange of tracer Sr2 in +

Sr-X76and tracer Cs+ and Rb' in Cs- and Rb-A77respectively involved a fast
process followed by a slow. They superimposed two diffusion equations and
analysed their rate curve to abstract two diffusion coefficients, one for the fast
exchange and one for the slow. In zeolite A there is only one channel system
although in the hydrated form two different types of cation sites are known to
c ~ e x i s t . This
~ analysis, therefore, suggeststhat the fast diffusion process involving
only the mobile, hydrated cations proceeds independently of the slow diffusion
process which involves those cations firmly bound to the lattice sites. Since both
diffusion fluxes must progress through the same k i n g s of 0-4nm free diameter,
it is dficult to imagine them being independent of each other. Hoinkis and Levi
also studied Ba2+ tracer diffusion in Ba-A." Below 100°C they found a super-
imposed fast and slow diffusion, but above 100"Ctheir data fitted a simple single-
diffusion equation. They concluded that below 100°C diffusion involved both
sited and unsited Ba2+ ions whereas above 100°C very few ions could be con-
sidered as being sited. Hoinkis and Levi again interpreted their results as due to
two independent, superimposed, diffusion processes when they next studied tracer
diffusions in zeolite X. 7930 They assumed that the fast diffusion occurred through
the network of supercages and the slow one through the independent network of
sodalite and hexagonal prism channels.
Sherry and co-workers have proposeds9 a somewhat different mechanism to
explain the results of Levi et ul. and similar results obtained by them. They con-
sider a single, fast, diffusion process involving only the mobile unsited ions and a
simultaneous slow first-order, adsorption-desorption reaction between unsited

69 R . M. Barrer and L. V. C. Rees, Trans. Faraday Soc., 1960, 56, 709; Nature, 1960,
187, 768.
'
O R. M. Barrer, R. F. Bartholomew, and L. V. C. Rees, J . Phys. and Chem. Solids, 1963,
24, 51 ; 1963, 24, 309.
7 1 R . M. Barrer and L. V. C. Rees, J. Phys. and Chem. Solids, 1964,25, 1035.

'' L. V. C. Rees and A. Rao, Trans. Faraday SOC.,1966,62, 2103; 1966,62, 2505.
7 3 N . M . Brooke and L. V. C. Rees, Trans. Faraday Soc., 1968,64, 3383; 1969,65,2728.
7 4 E. Hoinkis, H. W. Levi, W. Lutze, N. Mickeley, and T. Tamberg, Z . Naturforsch,
1967, 22a, 220.
7 5 E. Hoinkis and H. W . Levi. 2. Narurforsch, 1968. 23a, 813.

7 h E. Hoinkis and H. W. Levi, Z . Nafurwiss., 1966, 53, 1.

7 7 E. Hoinkis and H . W. Levi, Z . Naturforsch, 1967, 22a, 226.

7 8 L. Broussard and D. P. Shoemaker, J . Amer. Chem. Soc., 1960, 82, 1041.

79 E. Hoinkis and H. W. Levi, 'Ion Exchange in the Process Industries', Society of Chemi-
cal Industry, London, 1970, p. 339.
E. Hoinkis and H. Levi, Z . Naturforsch, 1969, Ma, 151 1 .
 View Article Online

208 L. V. C. Rees
and sited ions. If this model is correct then the slow step should be independent of
particle size whereas in the model proposed by Hoinkis and Levi this rate should
be inversely proportional to the square of the particle size. Brown and Sherry59
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measured the slow rate of tracer diffusion in Na-X and Ba-X as a function of par-
ticle size and found no size dependency. Gaus and Hoinkis" modified the 'two
independent diffusing fluxes' model by including a first-order rate process for the
desorption of sited cations in zeolite A.
Dyer, Gettings, and Molyneux" measured the rate of Ba2+ tracer diffusion in
Ba-A at 19-45 "C and found that their results fitted a simple diffusion equation.
The first experimental points in their rate curves, however, were measured at
times when the fast process found by Levi et a/. would have been virtually com-
pleted. Dyer and get tin^^^,^^ studied tracer and ion-exchange kinetics in zeolites
A, ZK-4, X, and Y at temperatures well below 0 "C using methanol, ethanol, and
alcohol-water mixtures as solvents for the solution phase. They discovered that
Sr2 isotopic exchange in zeolite X is too slow to measure when methanol is the
+

solvent and methanol fills the zeolite channels, but that Ca2+and Ba2+exchange
could be measured. In zeolite Y (Si/Al ratio of 1.86)tracer exchange with all three
alkaline-earth ions could be measured in methanol, but in ethanol Ca2 and Sr2 + +

exchange was immeasurably slow. In another zeolite Y (Si/Al ratio of 2.60) tracer
exchange rates were quite fast for all three ions in both solvents. As the framework
charge decreases from X to 2.60 Y zeolite, the rates of tracer exchange in both
alcohols increase, while the activation energy for diffusion decreases. For a
specific divalent ion and zeolite the rate of tracer exchange decreases in the order
water > methanol > ethanol while the activation energy increases in the order
water < methanol c ethanol. If these are true diffusion processes and the mea-
surements were following transport of unsited ions through the channels, the
above changes in solvent and framework charge density would not be expected to
have such pronounced effects. Finally, Na+ tracer diffusion was very fast in all
solvents except for the Na-A-ethanol system at - 45 "C.
Dyer and Gettinsg3also looked at the effect of change of framework charge
density on tracer diffusion rates in isostructural zeolites A and ZK-4. The Si/AI
ratio of A is unity whde that of ZK-4 is 1-33. The activation energies for Ca2 and +

Sr2 tracer diffusion are higher in ZK-4 than in A zeolite while the reverse is true
+

for Ba2 . The cations will be more highly hydrated in ZK-4 than in zeolite A and
+

these higher activation energies for Ca2 and Sr2+may represent the additional
+

energy required to strip these additional water molecules from these cations when
they jump through the 0.4 nm free diameter 8-ring in the channel network. Ba2 , +

because of its lower hydration energy, may not be so influenced. The size of the
activation energy for Ba2+ may be more dependent on the magnitude of the

' H. Gaus and E. Hoinkis, 2. Naturforsch, 1969, 24a, 15 1 1.

82 A. Dyer, R. B. Gettins, and A. Molyneux, J . Inorg. Nuclear Chem., 1968, 30, 2823.
83 A. Dyer and R . B. Gettins, J . Inorg. Nuclear Chem., 1970, 32, 319.
84 A. Dyer and R. B. Gettins, 'Ion Exchange in the Process Industries', Society of Chemical
Industry, London, 1970, p. 357; A. Dyer and R. B. Gettins, J . Inorg. Nuclear Chem.,
1970,32, 240 1 .
 View Article Online

Ion Exchange in Zeolites 209

coulombic interaction between cation and charged framework and would be
higher, therefore, in A than in ZK-4. However, if hydration energy is not so
important with Ba2' it is difficult to understand why in zeolite A its activation
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energy is the largest of the three ions. The coulombic term would be similar for
all three ions, and Ba2 is much smaller in diameter than the aperture of the 8-ring.
+

Dyer et aLg5 tagged Na-X, Na-Y (Si : A1 = 1.86 : l), and Na-Y (Si : A1
= 2.60 : 1) with 22Na tracer and then exchanged these samples at 25 "C with
solutions containing excess quantities of Ca2+,Sr", and Ba2+. They found that
with each zeolite approximately 16 Na' ions per unit cell could not be rapidly
exchanged. These partially exchanged samples were then subjected to repeated
heating to 200 " C in uucuo followed by ion exchange with their respective divalent
ion solutions at 25°C. After three such treatments the Na+ content was pro-
gressively reduced to a negligible quantity in each case. This confirms previous
ion-exchange and X-ray data (see Section 3) that 16 Na' ions per unit cell occupy
small cage sites in these zeolites and that alkaline-earth ions exchange either very
slowly or not at all with these N a + ions at 25 "C. However, on heating to 200°C
in uucuo these divalent ions do occupy these small cage sites but only in a random
manner, since it requires three heat and exchange treatments to produce the pure
divalent ionformsofthesezeolites. Thisinteresting observation implies that under
the conditions of dehydration (i.e. 200°C in uacuo) the divalent ions show no
great affinity for I'(or even less likely I) sites. Dyer et also demonstrated that
in the pure divalent ion forms of these zeolites the small cage sites are occupied
only to a level of 8 divalent ions per unit cell under the experimental conditions
(i.e. 200 "C in uacuo) although Sr-X is an exception to t h s result.
Tracer diffusion of water in analcite and synthetic Na-P zeolites has been mea-
sured by Dyer and Molyneux.86 The rates and energies of activation for exchange
of water in various zeolites are compared. In the compact zeolites the rates are
slower and the energies of activation larger than the corresponding quantities for
tracer exchange in ice. The water exchange rates do not seem to be affected by
concurrent ion exchange. The rates of water exchange were shown to be very
much slower than the rates of tracer diffusion of Na' ions in these compact
zeolites.
Using single spheres, Fischbach and Levis' have measured the rates and energies
of activation of diffusion of tracer alkali-metal and alkaline-earth ions in natural
chabazite. These resultsareinsatisfactoryagreement with previous data.'" From
electrical conductivity measurementsactivation energies for ion transport inNa-A,
Na-X, and (Mg,Na)-A have been obtained.88 Change in the water content had
little effect with (Mg,Na)-A but with Na-A the energy decreased then increased
as the degree of hydration increased. Information on the distribution and migra-
tion of exchangeable cations between various sites of zeolites X and Y was also

'' A. Dyer, R. B. Gettins, and J. G. Brown, J . Inorg. Nuclear Chem., 1970, 32, 2389.
Dyer and A. Molyneux, J . Inorg. Nuclear Chem., 1968, 30, 829, 2831.
'' A.
86
H . Fischbach and H. W. Levi, Radiochim. Acta, 1969, 11, 143.
88 B. A. Glazun, I . V. Zhilenkov, and M. F. Rakityanskaya, Zhur. $2. Khim., 1969, 43,
2397.
 View Article Online

210 L . V . C.Rees
derived from electrical conductivity data.89 The conduction was proved to be
ionic and the specific conductivity found to decrease in the order Cs > K > Ag
> Na > Li after samples had been heated to 430°C under vacuum. Activation
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energies in X were found to be lower than in Y for specific ions. The electrical
conductivity of these same zeolites in their Na, Ca, Mg, La, Y, decationised, and
mixed Ca-decationised forms has also been measured” and found to decrease
in the order Na > Divalent forms > Trivalent forms.
Binary Ion-exchange Kinetics. The only significant advance in this field is the
work of Brooke and Rees. 73*91 They have extended the treatment of Helfferich
and P l e ~ s e for
t ~ ideal
~ ion-exchangers to include all forms of non-ideality of the
exchanger. Their finite differencesolution of the diffusion equation can cope with
an interdiffusion coefficient which contains concentration, tracer diffusion coef-
ficient, thermodynamic non-ideality , and irreversible thermodynamic cross-
coefficient terms. Introduction of some of these factors has been to give
rates of the forward and backward exchanges:
A(Z) + B‘+ -+B(Z) + A*+
and
B(Z) + A’+ +A(Z) + Bz+
where A and B are the two ions of valency z+ involved in the exchange and (Z)
represents the anionic framework, which are the reverse of those given by the ideal
treatment and which are now in semi-quantitative agreement with experiment.
However, in other examples agreement between theory and experiment is still poor
and real agreement between these rates awaits the determination of an exact inter-
diffusion coefficient which includes all the factors listed above. In an interesting
theoretical paper Brooke and Rees’ have shown that useful information could
be derived from experimental studies of rates of forward and backward exchanges
usingstartingmaterials which contained various ratios of the two ions at zero time.
Related Studies-The permittivity and dielectric loss factor for zeolites K-A,
Na-A, Ca-A, and Ag-A as a function of the amount of adsorbed water can be
correlated to the movement of these cations within the cavities.93 The activation
energy for the dielectric loss process varies with the water content but at any one
water content a linear relationship between the activation energies and size of
cations exists. The water in the channels seems to freeze at a temperature well
below 0 C. O

A rapid, self-consistent, assessment of the location of probe Mn2+ ions in

zeolite Y has been made using e.s.r. s p e c t r o ~ c o p y The
. ~ ~ distribution of cation is
89 R. Schoonheydt and J. B. Uytterhoeven, Clay Minerals, 1969,8, 71 ; ‘Molecular Sieve
Zeolites’, 2nd Internat. Conf. Amer. Chem. SOC., Worcester, U.S.A., 1970.
90 K . V. Topchieva, 1. F. Moskovskaya, J. Nejnska, and L. T. Shirshova, Vestnik Moskou.
Uniu. (Khim.), 1970, 11, 147.
91 N . M. Brooke and L. V. C. Rees, ‘Molecular Sieve Zeolites’, 2nd Internat. Conf. Amer.
Chem. SOC.,Worcester, U.S.A., 1970.
92 F. Helfferich and M. S. Plesset, J . Chem. Phys., 1958, 28, 418.
93 B. Morris, J . Phys. and Chem. Solids, 1969, 30, 73, 89, 103.
94 T. 1. Barry and L. A. Lay, J . Phys. and Chem. Solids, 1968, 29, 1395.
 View Article Online

Ion Exchange in Zeolites 21 1

determined not only by the ionic charge and radius but also by the degree of
covalent character of the cation bonding. During dehydration, the bi- and ter-
valent ions concentrate in the sodalite cage sites due to the retention of water in
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these cavities. The e.s.r. spectra of NO adsorbed in zeolites Na-A, Ca-A, Na-X,
and H-Mordenite at 77 K have been analysed to derive crystal field splittings and
2pn levels.' The electric field gradients at various sites have also been established.
E.p.r. ~tudies'~of alkaline-earth forms of zeolite Y containing NO and 0,-
species have shown the existence of two types of sites in Mg-, Ca-, and Sr-Y, but
the one type of site in Ba-Y resembles that found previously in H-Y. In a similar
study NO and NO2 molecules were used as the paramagnetic probes" in both
alkali-metal and alkaline-earth forms of zeolites. Electron transfer from sorbate
to sorbent surface was observed. The paramagnetic centres produced by y-
irradiation of zeolite A in various cationic forms have been studied by e.p.r.
spectr~scopy.'~The n.m.r. spectra ofwater adsorbed in various cationic forms of
zeolites A and X indicate the existence of two types of proton^.'^ The mobility of
water molecules in Na-X was also studied by n.m.r. spectroscopy."'
Optical spectroscopy has been used to observe the effect of cation exchange on
the luminescence of anthracene sorbed in zeolite Y."' Both optical and e.p.r.
spectra have been analysed to determine the effect of dehydration on the octa-
hedral hexa-aquo complex of Cu2+in zeolite Y.'02 The visible spectra of Ni2+
ions in dehydrated zeolite A have been interpreted on the model of a site having
D,,(or D6),)symmetry of oxygen ligand~.''~The number and intensities of the
bands agree well with the01-y."~ There is also reasonably good agreement
between calculated and observed energy values. The effect of sorption of various
gases, including H 2 0 , on the Ni2+ spectra has been studied. However, the
Reporter does know of some unpublished work which found that Ni-A, like
Ba-A, collapses on partial dehydration at quite low temperatures.
Some recent i.r. studies have thrown further light on the nature of the cata-
lytically active sites in zeolites. Ion exchange affects the strength of the electro-
static field and acidity of these active centre^.''^ It was shown that the first
16 Ca2 or Mg2 ions exchanged into NH,-Y are located in the hexagonal prisms
+ +

after dehydration at 450°C.'06 The frequency of the 3650 cm- OH band was '
C. L. Gardner and M. A. Weinberger, Canad. J . Chem., 1970,48, 1317.
96 J . H . Lunsford, J . Phys. Chem., 1970, 74, 1518; K . M. Wang and J. H . Lunsford,
J . Phys. Chem., 1970,74, 1512.
97
A . G. Kotov. Yu. A . Breslav. and S. Ya. Pshezhetskii. Teor. ieskp. Khim., 1969.5, 367.
98 Yu. A. Breslav and A. G . Kotov, Khim. uysok. Energii., 1970,4, 149.
99 V . V. Mank, I . V. Matyash, M. A. Piontkovskaya, I. E. Neimark, and R. S. Tyutyunnik,
Zhur. strukt. Khim., 1970, 11, 12.
loo H. A. Resing and J. K . Thompson, 'Molecular Sieve Zeolites', 2nd Internat. Conf.
Amer. Chem. SOC., U S A . , 1970.
G . I. Denisenko, M. A. Piontkovskaya, and I. E. Neimark, Ukrain. khim. Zhur., 1970,
36, 260.
lo2 I . D. Mikheikin, V. A. Shvets, and V. B. Kazanskii, Kinetika i Katalir, 1970, 11, 747.
lo' K. Klier and M. Ralek, J . Phys. and Chem. Solids, 1968, 29, 951.
'04 R. Polak and V. Cerny, J . Phys. and Chem. Solids, 1968, 29, 945.
lo' J . W. Ward, J . Catalysis, 1970, 17, 3 5 5 .
'06 J. W. Ward, J . Phys. Chem., 1970,74, 3021.
 View Article Online

212 L. V . C. Rees
found to be dependent on the amount rather than the nature of the residual cation
in decationised X and Y zeolites. The frequency was interpreted in terms of the
electric field in the zeolitic cavities.'"
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Mossbauer spectroscopy has demonstrated that ferric cations in zeolites are

reduced to ferrous on dehydration under vacuum. '08 Similar studies have shown
at this redox reaction is rever~ible.'~'The environment of the iron cation has
:en postulated and the effect of adsorbed species on the spectra s t ~ d i e d . ' ~ ~ . ' ~ '
D.t.a., t.g.a., and dilatometric methods have been used to determine the thermal
stability of various ion-exchanged forms of zeolite A ;'l o Na-A, Na-X, Na-Y, and
''
severalnaturalzeolites;' andzeolitescontaininggermaniumintheframework. ''
The lattice constants of various zeolites after thermal pretreatment have been
used to ascertain the thermal stability of these zeolites.' '
Unit cell constants,
refractive index, density, and chemical composition of 28 different samples of
chabazite have been reported' l 4 and d.t.a. of 3 of these samples was also included.
The 'a' and 'c' cell constants were correlated to Si : (Si + A1 + Fe) ratios and
total concentration of exchangeable cation. The ratio of sum of monovalent ion
content to sum of total exchangeable cation was related to the refractive index.

lo' R . Schoonheydt and J. B. Uytterhoeven, J . Catalysis, 1970, 19, 55.

J. Morice and L. V. C. Rees, Trans. Faraday Soc., 1968, 64, 1388.
lo' W . N. Delglass, R. L. Garten, and M. Boudart, J . Chem. Phys., 1969,50,4603; W. N .
Delglass, R . L. Garten, and M. Boudart, J . Phys. Chem., 1969,73,2970; W. N . Delglass,
R. L. Garten, and M. Boudart, J . Catalysis, 1970, 18, 90.
M. Murat, M. Mange, J. L. Thomas, and C. Eyraud, Chirn. analyt., 1970, 52, 57.
I I M . Murat, Compt. rend., 1970, 270, D , 1657.
"* E. Hauser, H. Nowotny, and K . J. Siefert, Monarsh., 1970, 101, 715.
'IJ E. Pecsi-Donath, Acta Mineral. Petrogr., 1968, 18, 127.
l4 E. Passaglia, Arner. Mineralogist, 1970, 55, 1278.