7.

Acid catalysis

A variety of chemical transformations are catalysed using acids. These include inter alia
reactions such as cracking, oligomerisation, isomerization, etherification, esterification,
etc. Heterogeneous catalysts can be employed, if the surface of these materials
possesses an acid site of sufficient strength to catalyse the reaction. The advantage of
using heterogeneous acids instead of classical acids is the ease of separating them from
the product stream and avoiding the need to deal with corrosive streams. An inherent
disadvantage of the use of heterogeneous catalysts is the deposition of coke onto the
solid, which may lead to catalyst deactivation.

7.1 Acid strength

Two types of acids can be defined, viz. Brønsted acids and Lewis acids. A compound
can be defined as a Bronsted acid if it can donate a proton to a base. In general, the
interaction between a Bronsted acid (HA) and a base can be described as:
HA + B ⇋ A− + HB +
The donation of a proton from an acid (HA) results in the formation of the conjugated
base (A-) and the addition of a proton to a base (B) results in the formation of a
conjugated acid (HB+). The classical example is for instance the interaction of mineral
acids with water. For example the interaction of hydrochloric acid with the base water
can be described as:
HCl + H O ⇋ Cl− + H O+
Here, the chloride ion (Cl ) is the conjugated base of the acid HCl and H3O+ is the
-

conjugate acid of the base H2O. Hydrochloric acid is a stronger acid than H3O+, and
water is a stronger base than the chloride ion. Hence, the proton transfer is favoured.

It must be realised that other molecules may accept also protons. For instance, ethene
acts as a base in its interaction with hydrofluoric acid:
HF + CH = CH ⇋ F − + CH − CH +
It is well known that water can act as an acid and as a base. However, other compounds
show the same behaviour. For instance, in the interaction of glacial acetic acid with
sulphuric acid acetic acid takes on the role of the base [2]:
+
H SO + CH COOH ⇋ HSO− + CH C OH

The interaction of an acid with a base is thus strongly dependent on the base. Hence,
the acid strength of a compound can be defined as the tendency to protonate a certain
base [3] (note that this definition differs from the classical definition of Brønsted acidity,
which is defined as the ability to donate a proton). The acid strength is thus for a mono-
acid compound given by the interaction of the proton with a certain base (B)
H + + B ⇋ BH +
The equilibrium constant for the addition of the proton to the base is given by:
[B]
⁄f
B
a H+ ∙ a B [B] fBH+
Ka = = a H+ ∙ + = ∙ a H+ ∙
[BH ] +
aBH+ ⁄f + [BH ] fB
BH

[BH + ] fBH+
−log K a = log − log (aH+ ∙ )
[B] fB
[BH + ]
−log K a = H0 + log
[B]

174
 BH+
With H0 the Hammett acidity function H0 = −log aH+ ∙
B

For dilute, aqueous systems, the Hammett acidity function becomes equal to the pH of
the solution (since the fugacity ratio tends to 1). The Hammett acidity function of an acid,
which depicts the ability of a compound to donate a proton to a certain base, is
dependent on the composition of the solution. Figure 7.1 shows the Hammett acidity
function of some mineral acids with water as a base as a function of the mole fraction of
acid in the solution. The Hammett acid function is at low mole fraction of the acid the pH
of the solution. The various mineral acids show different Hammett acid function values
indicating that the tendency to protonate water of these different mineral acids is
different. At low mole fractions, the Hammett acidity function follows the well-known
order of acid strengths, i.e. HNO3 > HClO4 ≈ H2SO4 > HF. At intermediate mole fractions,
the Hammet acidity function is lower for HClO4 and H2SO4 in comparison to HNO3 (and
thus the tendency to protonate water is higher). A high mole fraction of the acid, the
tendency of HF to protonate water is larger than that of HNO3, i.e. HF is the stronger
acid with this base.

12
Hammett acidity function,

H2SO4 [3,4]

8
HF [5]
-H0

HClO4 [3]

4 HNO3 [6]

0
0 0.2 0.4 0.6 0.8 1
Mole fraction of acid in acid-water mixture
Figure 7.1: Hammett acidity function for some mineral acids in water as a function of
the mole fraction of the acid in acid-water solutions

The acidity can also be defined in terms of the ability of a Lewis acid to accept a free
electron pair from a base (Lewis acidity) [7]. By definition, the Lewis base must contain
an electron pair which can bond with a Lewis acid. The interaction between a Lewis acid
(A) and a Lewis base (:B) can be formulated as:
A+: B ⇋ A: B
Typical examples, of Lewis acids are BF3 and FeCl3:
BF +: NR ⇋ F B: NR
FeCl + Cl− ⇋ FeCl−
(and amines and chlorine are then Lewis bases, as well as Brønsted bases). The
strength of the various Lewis acids can be determined in terms of the Gibbs free energy
for the association reaction of a Lewis acid with a Lewis base. Laszlo and Teston [8]
classified the Lewis acidity of the various compounds for their interaction with
crotonaldehyde using computational methods. Christe et al. [9] classified various

175
materials for their tendency to coordinate with fluorine (F-). The strength of the Lewis
acids follow the order SbF5 > AlCl3 > AsF5 > PF5 > BF3.

The combination of a Lewis acid with a Brønsted acid may yield a superacid (a super
acid is defined as an acid with a lower Hammett acidity function than pure sulphuric acid
[10]). Both the Lewis acid function and the Brønsted acid function are defined in terms of
their equilibrium. The use a common base in a mixture of a Brønsted acid with a Lewis
acid (i.e. a Brønsted acid, whose conjugated base is also a Lewis base) higher tendency
to protonate:
Brønsted acid: HAB øn ⇋ H + + A−B øn
Lewis acid: AL wi + A−B øn ⇋ [AL wi − AB øn ]−
+ ]−
Overall: HAB øn + AL wi ⇋ H + [AL wi − AB øn

Table 7.1 shows some examples of these superacids, i.e. acids with a Hammett acidity
function less than that of sulphuric acid. The strong acidity of these superacids implies a
rapid rate of transfer of the acidic proton from anion to anion according to the Grotthus
mechanism (similar to the acidic proton in water) [11] indicating a loose bonding with the
proton enabling the addition of the proton to weak bases.

Table 7.1: Hammettt acidity function, H0, for some superacids [12]
Acid H0
H2SO4 -11.93
HSO3F -15.07
HF -15.1
HF/BF3
HCl/AlCl3
HSO3F/SbF5 -18.95
HF/0.5% SbF5 -21

Superacids protonate a variety of very weak bases including methane and other
saturated hydrocarbons (and even molecular hydrogen undergoes proton-deuterium
exchange in superacidic media) [13]. Superacids are also very effective catalysts for a
variety of electrophilic transformations of saturated and aromatic hydrocarbons.
Superacids such as CF3SO3H and HSO3F catalyse isomerization and alkylation
reactions of hydrocarbons (and thus also the reverse reaction of acid catalysed
cracking). Such reactions are of substantial practical interest to obtain high octane
petrol.

7.2 Heterogeneous acids

Although we typically think about acids in terms of homogeneous acids, solids can also
donate protons (Brønsted acid) or accept electron pairs (Lewis acid) and thus act as a
heterogeneous acid. Materials, which are able to act as a Brønsted acid, are in principle
all oxides containing surface hydroxyl groups [14], but also specific materials such as
resins (cross-linked polymer) with acid-groups attached to its back-bone structure [15]
(see Figure 7.2).

176
 H+

Figure 7.2: Basic unit of sulfonated polystyrene in its basic form, an acid resin (adapted
from Dardel [15]).

Strong acids are obtained by isomorphic substitution of a cation in an oxidic structure

with a cation of a different valency. For instance, the substitution of a silicon cation (Si4+)
in a silicate structure with a tri-valent ion, such aluminium (Al3+) will render the structure
negatively charged. This charge must be balanced by cations, e.g. protons. The
substitution of aluminium into an amorphous silica structure will result in the formation of
amorphous alumina-silicates. Alumino silicates can be represented by the general unit
cell formula [16]:

M
z  

x/z  2 x
 
AlO  SiO
 
2 y 
 nH O
2
where z is the valence of the charge compensating cation Mz+ (which can be H+, Na+, K+,
Mg2+, Ca2+, Ba2+ or La3+). The ratio of x/y is smaller than or equal to 1 as there are no
linking Al-O-Al bridges in aluminosilicate frameworks (known as the Löwenstein rule)
[17].

7.3 Zeolites
The crystal structure of zeolites is based on an infinitely extending three-dimensional
network of SiO4 and AlO4 tetrahedra (primary building units) thereby sharing all the
oxygen atoms. Each shared AlO4 tetrahedron in the framework bears a negative charge,
which is balanced by a positive charge from a cation (see unit cell formula). In most
zeolite structures the primary building units are assembled into secondary building units,
which are simple polyhedra such as cubes, hexagonal prisms or octahedral (see Fig.
7.3). The final zeolite structure consists of an assembly of these secondary building units
(see Figure 7.4 and Figure 7.5). As a result of this structural build-up of zeolites, all
atoms within a zeolite structure are at the surface, i.e. in direct contact with the fluid
phase.

Zeolites have a well-defined, regular void or channel structure of molecular dimensions.

The cations within the zeolite framework are mobile and can undergo ion-exchange. The
water can be removed reversibly by heat treatment, which leaves the framework
structure intact with micropores and voids, which can account for up to 50% of the
crystal’s volume [18]. Zeolites may have supercages, which are larger void spaces within
the crystallite that can only be accessed through relatively narrow windows (see Fig. 7.4
and Figure 7.5).

177
Figure 7.3: Secondary building units identifiable in zeolite frameworks [19]

Zeolite LTA (Linde A): 8 T atoms, channel diameter: 3 - 4 Å

Zeolite MFI (ZSM-5): 10 T atoms, channel diameter: 5.3 × 5.6 Å and 5.1 × 5.5 Å
Figure 7.4: Structures of some zeolites

178
 Zeolite MOR (Mordenite): 8T/12 T atoms, channel diameter: 6.9 Å

Zeolite MWW (MCM-22): 10T/12 T atoms, channel diameter: 5.4/7.0 Å

Zeolite BEA (Beta): 12 T atoms, channel diameter: 7.1 × 7.3 Å

Zeolite FAU (zeolite Y): 12 T atoms, channel diameter: 7.1 × 7.3 Å

Zeolite CLO (cloverite): 8/20 T atoms, channel diameter: 7.1 × 7.3 Å

Figure 7.4 (cont): Structures of some zeolites (a full review of different zeolite
structures can be found on the International Zeolite Association webpage
[20])

179
 (a) (b)
Figure 7.5: Schematic of the pore structure in zeolites [20,21]
(a) Pore structure of zeolite ZSM-5
(b) framework structure of zeolite Y

Zeolite’s framework structures are based on an infinitely extending three-dimensional

network of SiO4 and AlO4 tetrahedra (primary building units) thereby sharing all the
oxygen atoms. Each shared AlO4 tetrahedron in the framework bears a negative charge,
which is balanced by a positive charge from a cation (see unit cell formula). The cations
are mobile and can undergo ion-exchange. Water present in the zeolite structure can be
removed reversibly by heat, which leaves the framework structure intact with micropores
and voids, which could account for up to 50% of the crystal’s volume [18]. The silicon
and aluminium atoms in the zeolite framework are referred to as T atoms and the
framework density of the zeolite, usually expressed as T atoms per 1000 Å 3, is a
measure for the void volume. The lower the framework density, the higher the void
volume (e.g. zeolite Y – 12.7 T atoms per 1000 Å3 and zeolite ZSM-5 – 17.9 T atoms per
1000 Å3 [20]).

Zeolites are frequently classified according to the number of T atoms in the rings that
form the structure of the channels or of the windows between the voids. These may
range from very small (8 T atoms, 3 - 4 Å channel diameter viz. Linde A) to very large
pore zeolites with up to 20 T atoms in the ring (viz. Cloverite – 13.2 Å channel diameter).
The channel system of zeolites may be one-dimensional (non-connecting parallel pores
e.g. ZSM-12), two-dimensional (e.g. MCM-22) or three-dimensional (e.g. Beta). These
channels may interconnect (e.g. Beta) or be independent of each other (e.g. MCM-22).
ZSM-5 contains two one-dimensional channel systems which have different orientations.
They are interconnected in a way that the total channel system is effectively three-
dimensional (see Figure 7.4 and Figure 7.5).

In zeolites where supercages are present (e.g. zeolite Y, see Figure 7.5) or where the
channels intersect (e.g. ZSM-5), the primary products can be determined by the void
space left in these supercages or channel intersections. The diffusion of these primary
products and consecutive reactions then depend on the dimensions of the channels. For
example, ZSM-5 has 10 membered ring channels (5.3 × 5.6 Å and 5.1 × 5.5 Å)
intersecting with some offset and gives rise to a void space at the intersection with a
diameter of 9 Å [9, 10]. The void allows the formation of bulkier molecules than what was

180
possible in the 10 membered ring channels. The diffusion of these “bulkier” molecules in
the pore system is then depended on the size of the channels.

7.3.1 Zeolite synthesis

Natural zeolites are found in cavities in basic volcanic or metamorphic rocks. Although
natural zeolites have many applications they are not suitable for catalysts as they
contain impurities and are too scattered in location for any large scale exploitation.
Inconsistent quality is another decisive shortcoming of natural materials [22].

Synthetic zeolites are made hydrothermally under autogeneous pressure. The

hydrothermal synthesis of aluminosilicate zeolites corresponds to the conversion of a
mixture of silicon and aluminium compounds, alkali metal cations, organic molecules and
water via an alkaline supersaturated solution into a microporous crystalline
aluminosilicate as depicted in Figure 7.6 [23]. Common silica sources are colloidal silica,
waterglass, pyrogenic silica or silicon alkoxides (such as tetramethyl or tetraethyl
orthosilicate). These silica sources differ in the degree of polymerization of the silicon
dioxide. Aluminium sources are gibbsite, pseudo-boehmite, aluminate salts or the metal
powder. Cationic or neutral organic molecules are added to the synthesis gel as solvents
or structure directing agents (known as templates). Examples of templates are
hexamethyleneimine for zeolite MCM-22, tetraethylammonium hydroxide for zeolite Beta
and tetrapropylammonium hydroxide for zeolite ZSM-5 [24]. The alkalinity of the
synthesis gel may be controlled by addition of a mineralizing agent, for example sodium
hydroxide.

precursors

SDA SDA
extended
Reactants structures
gelation
Si, Al, SDA
Na, … OH-
Sources crystal

amorphous gel

Figure 7.6: Schematic representation of the zeolite formation process (SDA = structure
directing agent) [23].

A mixture of the silica source, aluminium source, template and mineralizing agent rapidly
forms a hydrogel or precipitate. Often the hydrogel must be aged, at room temperature
or slightly higher temperatures, to increase the concentration of precursor species

181
(secondary building units) in the hydrogel. This ageing of the gel is often crucial to
obtaining the desired crystalline phase and to improve or accelerate crystallization [25].

The crystallization process consists of the dissolution of the hydrogel, mediated by a

mineralizing agent, which provides the solution with silicate and aluminate monomers
and oligomers. These monomers and oligomers condense into specific precursor
structures, which are then organized into more extended structures and finally into the
crystalline phase [23]. To start the synthesis, the hydrogel is brought to crystallization
temperature, between 60°C and 200°C (under autogeneous pressure), and left for a
period of time to achieve an acceptable yield of crystals [25].

After a sufficient yield of the crystals is obtained, they are separated for the mother liquor
by filtration or centrifugation. The zeolite crystals are then washed to remove excess
unreacted reagents and dried at around 100 – 120°C. This form of the zeolite is known
as the “as-synthesized” zeolite. The zeolite contains both cations and the organic
template, which are blocking the zeolite pores. The organic template is removed from
the zeolite by thermal treatment in air, typically around 500°C. The cations are then
removed by repeated ion-exchange by a mineral acid or an ammonium salt solution
(most commonly used is ammonium hydroxide). This salt replaces the cations with
ammonium ions. Under thermal treatment, typically around 500°C, ammonia is released
from the zeolite leaving a proton. The zeolite is now active for acid catalyzed reactions
and is commonly written as “H-zeolite”.

Zeolite formation occurs in systems that are very far from equilibrium. This means that
the zeolite formation is very dependent on the initial and boundary conditions. That is,
the compositions of the synthesis gel, synthesis temperature and time, gel aging and
agitation. The zeolite structures formed are in many cases metastable. That is, with
increased synthesis time, the structures may recrystallize to other more stable structures
(often not the desired product). This is known as the Ostwald’s rule of successive
transformations.

7.3.1.1 Crystallization process of zeolite formation

The crystallization process of zeolite formation can be divided into three steps [23]:
 achievement of supersaturation
 nucleation
 crystal growth

Achievement of supersaturation
A solution with a specific concentration and temperature can be in a stable, metastable
or labile condition as shown in Figure 7.7 [23,26]. The stable and metastable areas are
separated by a single boundary curve, which determines the normal equilibrium
saturation concentration of the solute. The boundary between the metastable and labile
regions is not well defined and is indicated by the shaded area in Figure 7.7. the solution
changes from stable to metastable to labile upon increasing the solute concentration at
constant temperature (shown by the arrow in Figure 7.7),. This is known as
crystallization via supersaturation [26]. In terms of crystallization, no nucleation or crystal

182
growth occurs in the stable region and only crystal growth occurs in the metastable
region while spontaneous nucleation and crystal growth will occur [23,26].

During ageing, or especially at elevated temperatures, the concentration of the

aluminosilicate precursor species increases with time by dissolution of the amorphous
solid phase and interconversions of the dissolved aluminosilicate oligomers in solution
[23]. This process is the same as shown by the arrow in Figure 7.7 and so crystallization
of a zeolite occurs via the formation of a supersaturated solution.

labile
Concentration of solute

metastable
stable

Temperature of solution
Figure 7.6: The solubility - supersaturation diagram [23,26].

Nucleation
There are two types of nucleation – primary and secondary. Primary nucleation occurs
from a supersaturated solution can be homogeneous and heterogeneous.
Homogeneous primary nucleation occurs spontaneously while heterogeneous primary
nucleation is induced by impurities or foreign particles in the synthesis solution.
Secondary nucleation occurs when zeolite crystal seeds are added to the synthesis
solution [23].

Before the formation of viable nuclei i.e. nuclei on which crystal growth occurs
spontaneously, chemical aggregations of the aluminosilicate precursors form unstable
germ nuclei which then disappear through depolymerization. These fluctuations will
result in the germ nuclei increasing in size with time and such will lead to nuclei with the
critical dimensions to become viable and so spontaneous crystal growth will occur
[22,23].

The net Gibbs free energy of formation of a viable nucleus composed of j aluminosilicate
units can be expressed as:
ΔG j   Aj  Bj 2/3

183
where A and B are constants [22]. The first term represents the free energy of formation
of a nucleus composed of j aluminosilicate units. The second term represents the
interfacial free energy between the nucleus and the surrounding medium, which is
proportional to the surface area of the nucleus and has a positive value corresponding to
the destabilisation of the nucleus [22,23]. At small values of j, the net free energy of
formation of the nucleus is positive in sign, as Bj2/3 > Aj. This means at initially the
nucleus are thermodynamically unstable as shown in Figure 7.7. However, as Aj
increases more rapidly than Bj2/3 so the free energy of formation passes through a
maximum value and then decreases with increasing j. Once the nucleus has passed
over the maximum it will grow spontaneously. The maximum in the free energy of
 
formation is determined by d ΔG j dj  0 . The addition of further aluminosilicate units to
the nucleus will decrease the free energy of formation and favour crystal growth [22,23].

∆Gj

0
j
Figure 7.7: Representation of the free energy of formation, ∆Gj, of a nucleus
composing of j aluminosilicate units as a function of j [22].

The relationship between free energy of formation and supersaturation is illustrated for a
spherical nucleus [26]:
16πσ 3 MW 
2

ΔG  
3RTρ ln S 
2

where σ is the surface energy of the nucleus, ρ is the density of the nucleus and MW is
the molecule weight of the nucleus. From the equation above it can also be seen that at
saturation (S = 1) no spontaneous nucleation can occur as ∆G is very large whereas for
a supersaturated solution (S > 1), ∆G has a finite negative value and so spontaneous
nucleation can occur [23,26].

The number of viable nuclei formed per unit time is expected to increase with time
especially at the beginning. Various expressions have been derived for the nucleation
rate, J. The most common expression is in the form of the Arrhenius equation [26]:
 ΔG 
J  A exp   
 RT 

184
Substituting the equation for the free energy of formation in terms of supersaturation in
the above equation results a relationship that predicts an exponential increase in the
nucleation rate with increased supersaturation (this is shown in Figure 7.8 curve A).
However, curve B in Figure 7.8 shows the experimentally observed relationship between
the rate of nucleation and supersaturation. The nucleation rate increases and then
reaches and maximum and then decreases with increasing degree of supersaturation.
This decrease in the nucleation rate has been attributed to the increased viscosity of the
synthesis solution at high degree of supersaturation, which inhibits molecular migration
[23,26].

J
A
B

Scritical

S
Figure 7.7: Nucleation rate, J, versus degree of supersaturation (S) (curve A is
according to Arrhenius rate equation, curve B corresponds to experimental
observation) [26].

Crystal growth
Zeolite crystal growth occurs at the crystal-solution interface by condensation of
dissolved species (secondary building units or more extended units) onto the crystal
surface [22]. Nucleation and crystal growth consume the same precursor species,
therefore as the same time both processes will start to compete for these species. Thus
the nucleation rate will pass through a maximum in time and then decline.

The crystallization curves are in many zeolite syntheses sigmoid in shape as illustrated
in Figure 7.8. The inflection point of these sigmoid curves separates the autocatalytic
growth period with that delayed growth owing to a depletion of precursor species in the
solution [13].

Two observations can be made due to the completion between nucleation and crystal
growth. Firstly, the smaller the number of viable nuclei, the larger the average crystal
size will be found. Secondly, the completion between the nucleation rate and the crystal
growth rate will influence the crystal size distribution. That is, if the nucleation rate is
suppressed by crystal growth, the crystal size will be more uniform as the viable nuclei
have been growing as crystals for the same length of time. Whereas, if the nucleation

185
and crystal growth occur at the same time, the final crystal size distribution will be broad
as the viable nuclei have been growing as crystals for varying lengths of time.

Figure 7.8: Typical sigmoidal form of yield curves for zeolites.

The rate limiting step for crystal growth can either be the diffusion of the precursor to the
crystal-solution interface or the surface kinetics of the condensation of the precursor into
the crystal [27]. By studying the linear crystal growth rates of silicalite, it was seen that
the growth rates was similar (in the range of 0.036 – 0.04 μm h-1 [27]) for different
synthesis procedures. The activation energy of linear zeolite crystal growth was also
studied for a range of zeolites and found to be in the range 45 - 80 kJ mol-1 [27]. The
magnitude of the activation energies indicates that crystal growth is controlled by surface
kinetics rather than diffusional transport [27].

Factors influencing zeolite crystallization

Factors that can influence zeolite crystallization are:
 Composition of the synthesis gel,
o The SiO2 and Al2O3 sources, ratio and concentration;
o OH- concentration;
o Cations or anions present in the gel;
o Water concentration;
o Type of organic template.
 Synthesis time
 Synthesis temperature
 History of the synthesis gel, for example,
o Order of adding the synthesis reagents to the synthesis mixture;
o Gel aging;
o Stirring.

The influence of the synthesis gel composition varies according to the zeolite structure.
The effect of parameter changes can be studied through the identification of
crystallization fields in which zeolite are formed. For example, Figure 7.9(a) shows the
crystallization fields of various zeolites as a function of SiO2, Al2O3, and (Na2O+NH3) in
the organic-cation free synthesis of ZSM-5 [28]. There are three crystalline phases that
can be formed, namely, ZSM-5, Mordenite and a non-zeolite phase –quartz. In this
particular synthesis, the crystalline phase formed is more dependent on the synthesis

186
gel SiO2/Al2O3 ratio than the hydroxide concentration. At high silica concentration in the
gel, –quartz is formed whereas increasing the alumina in the gel leads to the formation
of first ZSM-5 and then Mordenite. Figure 7.9 (b) shows the interrelationship between
inorganic and organic cations. This tertiary diagram shows that both inorganic and
organic cations are required for the formation of ZSM-5 from this particular synthesis gel
as only amorphous material is formed from a pure organic cation synthesis. This tertiary
diagram also shows that large concentrations of Na+ in the synthesis gel, suppresses the
ZSM-5 crystallization and results in the formation of Mordenite [28].

Na2O + NH3
(a) ZSM-5
Mordenite
%
-Quartz
40

SiO2 40% Al2O3

K2O
(b)

ZSM-5
+
Harmotome
ite
en

ZSM-5
rd

ZSM-5
Mo

+ Amorphous
Na2O Analcime (TPA)2O

Figure 7.7: (a) Reaction mixture compositions and products formed in the synthesis of
ZSM-5 in the absence of organic template (b) Ternary composition diagram
for the Na2O-K2O-(TPA)2O cation system, showing the stability areas of the
phases formed after 4 days from a reaction mixture of 10 (Na, K, TPA) 2O -
Al2O3 – 28 SiO2 - 750 H2O [28].

The synthesis gel SiO2/Al2O3 ratio will determine the elemental framework composition
of the crystalline product, but the alumina concentration will also determine the phase

187
that is formed [28]. For example, zeolite A and high aluminium faujasite only crystallize
in a very narrow range of SiO2/Al2O3 ratio, whereas ZSM-5 is known to crystallize over a
very broad SiO2/Al2O3 range including aluminium free synthesis (silicalite) [28].

Table 7.2 shows the effect of changing the zeolite SiO2/Al2O3 ratio on the physical
properties of the zeolite. For zeolites used in the catalytic applications, a higher
SiO2/Al2O3 ratio is more valuable as the higher the zeolite SiO2/Al2O3 ratio, the higher the
thermal stability and acid resistance of these catalysts. For zeolites used in the
adsorption or ion exchange applications, a decrease in the zeolite SiO2/Al2O3 ratio
increases the cation content producing an improved hydrophilic adsorbent or ion
exchange material.

Table 7.2: Effect of changing the zeolite SiO2/Al2O3 ratio on the physical properties of
the zeolite [28].
Increasing the zeolite SiO2/Al2O3 ratio:
 Increases acid resistance;
 Increases thermal stability;
 Increases hydrophobicity;
 Decreases affinity for polar adsorbates;
 Decreases cation content.
Decreasing the zeolite SiO2/Al2O3 ratio:
 Increases hydrophilicity;
 Increases cation exchange properties.

The alkalinity of the synthesis gel is also a key importance in the zeolite synthesis. The
primary role of the OH- ions is to depolymerize the amorphous aluminosilicate
particulates at an appropriate rate. The alkalinity has an impact on the crystallization
process, on the SiO2/Al2O3 ratio of the zeolite phase and also on the size of the final
zeolite crystals [23]. Table 2 lists the role of the hydroxide ion in the crystallization
process.

Table 7.3: Role of hydroxide ion in crystallization of zeolite structures [28].

 Functions as structure director through control of the degree of polymerization
of silicates in the solution;
 Modifies nucleation time by influencing transport of silicates from the solid
phase to solution;
 Enhances crystal growth by influencing transport between the solution phase
and the growing crystal;
 Controls phase purity through influencing the rate of transport of silicate
species from one crystalline phase to another.

The roles of the organic templates are:

 Structure-directing – defining the zeolite phase formed;

188
  Gel modifier – could allow the formation of structures with higher SiO2/Al2O3 ratio
than could be obtained without such additives;
 Interact chemically with the gel – altering the character of the gel (for example
alkalinity);
 Interact physically with the gel – modifying the solubility of various species, the
transport properties etc;
 Void filler.

The crystallization of a zeolite usually follows a crystallization curve (crystallinity as

defined by powder X-ray diffraction). A desired zeolite species is often a metastable
product that can undergo re-dissolution, while a more stable species is formed.
Therefore, synthesis times are important criteria to obtain a pure crystalline phase.

The synthesis temperature can determine the zeolite phase formed. A higher synthesis
temperature may favour a denser zeolite phase. Synthesis temperature also affects the
crystallization kinetics. Higher temperature may result in shorter induction periods or a
metastable species may decompose faster at a higher temperature.

The history of the zeolite synthesis mixture (order of adding of the synthesis reagents,
gel aging, stirring, etc.) can result in different crystallization kinetics, modification of
crystal composition or even the formation of a completely different zeolite phase.

7.4 Mechanism of acid-catalysed reactions

Olefins are weak bases and can be activated in the presence of (strong) acids. The
nucleophilic attack of an acid on an olefin results in the formation of carbenium ions. The
order of stability of carbenium ions is tertiary > secondary > primary > CH3+ [29]. The
carbenium ions can undergo further reactions:
intra-molecular reactions:
 [1,2] G-shift (G either H or alkyl; only if structure is non-constrained)
 Chain branching (via protonated cyclo-propyl cation intermediate).

(reactions such as double bond isomerization may occur via either a [1,2] G-shift or a
protonated cyclo-propyl intermediate; the former with a much lower activation energy)

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