Materials Chemistry and Physics, I?

(1987)

49-71

49

ZEOLITE ACIDITY DEPENDENCE ON STRUCTURE AND CHEMICAL ENVIRONMENT. CORRELATIONS

WITH CATALYSIS

D. BARTHOMEUF
Laboratoire de Reactiviti?de Surface et Structure, UA 1106, CNRS, Universite
Paris VI (France)
Received December 1, 1986; accepted January 10, 1987

ABSTRACT
The dependence of zeolite acidity on framework properties is studied first by
considering the parallelism existing between the proton acid strength and the
strength of the lattice Al-0 bond. The structure topology is more specifically
taken into account in the definition of an aluminum topological density TDAl
which evaluates the density of Al04- tetrahedra in a maximum theoretical number
of T04. It allows the estimation to be made for each structure of the limit Al
molar fraction (m = Al/Al + Si) below which none of the A104- is in a next nearest neighbor situation. This limit mNNN value determines the Al content below
which the efficiency of sites and their acid strength should be the highest and
should be constant. The values are lower for the topologicallydenser structures,
being ranked for instance for the usual zeolites as MFI < MOR < OFF < FAU. These
limit values make possible the calculation of the theoretical curves changes
with Al content in effective acid site number for different acid strengths. The
maxima of the volcano curves expected are shifted to lower Al contents for strorr
ger acidity and for denser structures. It follows that an estimation of the Al
molar fraction giving the maximum catalytic activity can be made for all the
structures which topological density is known. For the usual zeolites the values
are ranked in the same order as reported above. The Si/Al ratios at the maxima
are MFI (9.5) > MOR (9.4) > OFF (8.3) > FAU (6.8).
Finally the selectivity for the formation of light products in the cracking of
n-paraffins is related to a field gradient effect depending on the distribution
of charges in the space surrounding the molecules in the pores.

INTRODUCTION
The concept of acidity of solids is not perfectly understood. For protonic solid oxide catalysts the definition for instance of acid strength involves the
energy of the O-H bond which evaluation in the presence of adsorbed phase is not
as easy as that for example of a pKA for an acid in solution. An important
class of acidic solids consists of zeolites whose acidic properties are studied
both from fundamental and applied standpoints. The implication in catalysis is
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50

of major interest and a large amount of work is devoted to a better understandding of zeolite acid properties. The situation is rather complex with those aluminosilfcate catalysts since Al can be removed from the framework eitherby steaming [1,2] or by chemical extraction with EDTA [3,4], acetylacetone [5], SiC14
[6] or NH4SiF6 [7] without significant loss of crystallinity. The consequences
on acid properties can be particularly drastic since extraframeworkspecies deposited in the cavities may in some cases generate acidity.
In an attempt to clarify the zeolite acidity approach, in

a first step the

present paper will consider only framework sites, for zeolites with no defects
or occluded extraframeworkdeposits. It will be shown, in what manner, even in
this simple case an acid site cannot be considered independently from the structure it belongs to, i.e. from the topology and distribution of Al and Si atoms
in the TO4 tetrahedras. The consequences for catalytic properties will be pointed
out.

PARAMETERS CHARACTERIZING ZEOLITE ACIDITY

The well recognized parameters used to describe Lewis and Rrijnstedacidity
are the number and density of sites, their location, strength and also an effi-

ciency coefficient comparable to activity coefficients In solution.

The number of potential acid sites equals theoretically the number of Al
atoms. It may be decreased, for the protonic sites by exchange of protons by metal cations or upon dehydroxylationto give the actual number of protons. Simultaneously the number of Lewis sites consisting of metal cations or Al atoms increases. Any modification of the number of sites involving extraframework species will not be considered here.
The density of sites is usually not very well defined. Scientists using this
parameter assume implicitlythatit is a number of acid sites per unit volume or
unit mass. The distinction has to be made between the potential acid site number
and the actual number of sites. The first one,which equals the number of framework negative charges and depends only on the zeolite chemical composition,defines a density of charges, positive or negative, to which the electrostatic field
created in the cavities is related. The second one

expresses the number of ac-

tual acid sites in the experimental conditions used, &

after possible

exchange or dehydroxylation. It gives a density of actual acid sites which is an

average approach to the closeness of sites and is often used in the case of bimolecular reactions for instance which require two close protonic sites [81.
In addition to the density of sites a factor of major importance is the loeation of A104- tetrahedra generating the acidity. Whether Al are in accessible
cavities, paired or not, or are in T sites crystallographicallydifferent in
nature, etc. will change the intrinsic and the measured acidity. In recent

51
years large progress has been made in the knowledge of Al location mainly in
29
27
faujasite [9],using Si and
Al MAS NMR. Information is still very much needed
for structures other than faujasite with non equivalent T sites or with low Al
content such as mordenite or MFI.
For the Lewis and BrSnsted sites the acid strength can be defined in general
terms as the energy of the bond between the acid center and a base. In addition
for protonic acidity the strength can be expressed as the energy of the O-H bond
between the framework oxygen and the attached proton. Many methods have been developed to characterize the acid strength. None of them is able to give absolute values comparable to the scale of pKAfor acids in solutionfor instance.Usually
samples are ranked using one method. Care has to be taken in the definition of
the experimental conditionsused.For example a classical way to look at acid
strength is to determine it by means of infrared spectrometry or thermodesorption;
the upper desorption temperature at which a base is retained on BrGnsted and

Lewis sites. Ammonia and pyridine are widely used. In contrast with their pKA
sequence it is well known that pyridine is more strongly held

than

am-

monia. This results from the various interactions and molecules disturbances
created in the zeolite cavities by the framework charges which are different for
the two molecules, comparable to a solvent effect in solution [lo] and which
changes their basicity in the adsorbed phase.
Considering the high concentration of acid sites in zeolites of the order of
5 to 10 H+ per liter of crystal it has been proposed that,as in solution,activity coefficients should be considered. An efficiencycoefficienta0 [lO,ll] which
behaves as an activity coefficient [10,12] has been determined in faujasites.
This factor increases from CL = 0 for a faujasite with Si/Al = 1 where every Si
0

atom is surrounded by four Al atoms to a0 = 1 for Si/Al close to 6 where each

hexagonal prism contains 2 Al atoms, one in each face (131.
It was early proposed that the chemical environment of sites should affect
their acidic and catalytic properties [14]. This may result:i) from an influence
of close neighbors as in a solution molecule-moleculeinteractions disturb local
properties;or ii) from overall effects comparable to collective properties in
solutions (change with the concentration of the physical properties such as refractive index or density and of the chemical properties such as acid strength
expressed for instance by the Hammett Ho function)[lO,lS].
All the acidity parameters listed above are related to environment effects.
Some of those factors affect this environment. They are the number of sites,
their location and their density. Some others are modified by it, like the acid
strength and the site efficiency. Since the arrangement and distribution of
neighbors plays a significant role it follows that the structure and topology of
the zeolite should also be considered in

studying

those properties. In that sense

the cases of local and overall environment effects will be considered separately

in what follows.

52
DEPENDENCE OF ACIDITY ON LOCAL ENVIRONMRNT
The dependence of properties of a site on the nature of its close neighbors
has been first proposed in faujasites [i4]. This short range influence exists in
any structure. Each framework has its characteristic topology. In addition some
structures have several topologicallynon-equivalent T atoms, i.e. T sites not
crystallographicallyidentical 1161. For instance compared to the unique T sites
in faujasite, L zeolite has two, mordenite four and MFI

twelve non equivalent T

sites. This implies that in addition to an effect of local distribution of Al

and Si atoms around a given TO4 tetrahedron the properties may also be affected
by the topological T site under consideration since the angles and distances and
hence interactionsbetween neighbors will be different.
The case of four different zeolites, faujasite, mordenite. L and MFI

will be

considered separately.

Faujasite
Despite the fact that all the T sites are topologicallyequivalent a large
number of results show that they are not chemically identical, i.e. the reactivity of atoms in those sitesvary with their environment.
First evidence is provided by the experimental fact that approximately 20
Al atoms per unit cell in Y zeolite can be removed much more easily than the 3536 remaining ones,either by steaming [17] or chemical extraction 114,181. The
corresponding limit of Al molar fraction Al/Al + Si is 0.18 (X/Al = 4.5). As an
example acetylacetone cannot remove more than 19-21 aluminium per unit cell
14,181.

[ll,

The same limit appears in more recent work using SIC14 with the special

feature that by contrast this reactant removes completely and preferentially those
weakly bonded Al atoms in any extraction [19]. When present in the structure
those Al atoms generate properties different from those arising from the more
strongly bonded aluminium. For instance their removal decreases neither the number of strong acid sites nor the isooctane cracking as shown in Figure 1 [5,11,
14,201. Preliminary results suggested that environment in T sites could vary, generating weakly or strongly bonded Al, each of them giving rise to a different
acid strength 1141. Weak framework Al-O bonds would leave the oxygen orbitals
available to form a strong O-H bond, -i.e. to give rise to weak acidity.
Several models have been proposed to account for the effect of the number of
Al neighbors on acidity [Zl-251. Their common hypothesis is thatstrong acidity
arises from A104- tetrahedras with no close Al neighbor in the second layer of T
sites. The main conclusion from all those calculations is the presence of a maximum in the number of strong acid sites with no next neighbor in the range 30-40
29
Si MAS NMR is an extremely
Al per unit cell i.e. Si/Al varying from5.4to 3.8.

53
helpful tool to determine the Al distribution in the T sites [9,26]. Results
showed that an ordered rather than a statistical distribution of Al atoms occurs.
Correlation can be found between the presence of Al atoms with no close neighbor
and the acid strength [23].

20

0.1

0.2

Al/Al+Si

Fig. 1. Changes in acidity (a) and isobutene formation in isooctane cracking at

573 K (b) as a function of Al molar fraction m = Al/(Al * Si), in faujasites.
Extracting agent : n,

0, EDTA ;R,O,

minopentacetic acid ;U

,@

acetylacetone ; a, @ , diethylene tria-

, diaminocyclohexaneN,N,N',N', tetracetic acid

(from ref. 5,11,14,20).

Applying those results to catalysis is not straightforward.Removing Al from

the framework changes the number of close neighbors. This is taken into account
29
Si MAS NMR but defects such as holes may be
in models and this is observed in
created and extraframework deposits may be formed. They are not considered in
the models. They may greatly change the catalytic properties through diffusion
effects or modification of strengthand of the actual number of acid sites. Due
to those perturbations, for similar average framework environments, the catalytic activity of a given site might vary in a large range. Those reasons might explain
the apparent discrepancy noted between several authors for catalytic properties
in the range N 30-56 Al per unit cell (Si/Al w 5.5 to 2.5). In fact three completely different dependences have been reported as the Al content decreases, a
constancy [11,14, Fig. 11, an increase [19] or a decrease [27,28] in catalytic
activity. Those results have been obtained from samples dealuminated in different ways and for different experimental catalytic conditions. By contrast there
is a very good agreement in the literature about the smooth decrease in catalytic properties which parallels the number of framework Al atoms in the range
25-O Al/u.c. [11,14,19,27-29,Fig. 11. This tends to indicate no major change in
acid strength below 30-25 Al/u.c. (Si/Alru 5.4-6.7).

54

A more detailed
pological

approach

configurations.

ted by AlO4-

tetrahedras

next nearest

neighbor

requires

the absence

nity. This occurs

of local framework

In addition

environment

with no other Al atoms within

referred

at high

cation exchange

level or at low Al content.

of NNN tetrahedra

irrespective

It is 9 for faujasite

topology.

instance.

the chance to have two protons

at a higher Al or Na content
calculation

in faujasite

gave for Y an aluminum

below which all the protons

pend on each structure

i.e. no Al

[25] says that strong acidity

+
metal cation such as Na in the NNN vici-

pends on the structure

Consequently

four bonds,

are genera-

to as NNN, Wachter

of any buffering

more at any T sites the number

effect is based on to-

to the idea that strong protons

and 12 for mordenite

in a NNN situation

than in mordenite.

concentration

should be strong

Further-

of Si or Al defor

occurs

Several methods

of

of 23 to 32 Al per unit cell

[25]. Such limit values would de-

topology.

It can be noted that the above given results coming either from experiments
[14,18,19,27,28]
unit cell

or from theoretical

[21,25] give a range 23-40 Al per

(Si/Al 7.3 to 3.8) for the limit below which A104-

strong acidity.
gly chemically

This also corresponds

neighbors

tetrahedra

to the number already mentioned

bonded Al atoms in the framework

idea that the strength

of the proton varies

[11,14,17,18].

generate
of stron-

It reinforces

the

not only with the number of close

but also with the energy of the Al-0 bond. Oxygen atoms strongly

ked to the Al framework

strongly

models

atoms will retain weakly

the protons which

lin-

then become

acidic.

Mordenite
It is known for a long time that aluminum
mordenite
acidity

by acid treatment

strength

are not only related

type of T site involved

dy of changes

or steaming.

red to

evidenced

'1' and

catalytic

properties

tion results

acid extraction

a selective

could attack

approach

removal

the series

applied

[31,32]. Figure

the following

tion removes Al atoms from type

ty and not to BrGnsted

acidity.

in

but rather to the

For instance

a detailed

treatment

stu-

conditions,

the different

T sites spe-

to HCl dealuminated

of Al from two different

2 shows the different

mordenites

studies using IR spectroscopy

allowed

from

changes

or stea-

sites refer-

1 to 4 of the T sites giving rise to different

for the two types of modified

tailed acidity
pyridine

'2' in

Al content

extraction.

a, b, c with chemical

cifically or sirmltaneously [30].This

med samples

to a specific

in the aluminum

in lattice parameters

showed that hydrochloric

can be very easily removed

By contrast with faujasite,

conclusions

toluene disproportiona-

[31,33]. In addition

and thermodesorption

de-

of ammonia

and

to be drawn. At first HCl dealumina-

'1'. They are related

They are not involved

to the strong Lewis acidiin the toluene

dispropor-

by acidic OH groups. The Al '2' atomsare related to

-1
hydroxyls. They are responsible for the
BrGnsted acidity giving the acidic 3600 cm
tionation.

They are replaced

55

high catalytic deactivation. They are removed by steaming and replaced by Si

atoms. The steaming creates simultaneouslynew strongly acidic active sites and
catalytic properties are increased [32,34].

100

time (min.

Fig 2. Toluene disproportionationin mordenite at 723 K as a function of time on

stream.
Dry air pretreatment at 773 K (a) and steaming at 773 K (b) of mordenite Norton
zeolon 900 (O,o)

and HCl dealuminated (m

,n

)(from ref. 32,33).

This example and more recent studies [35,361 show how complex can be the mordenite synthesis and further Al extraction because of the importance of local
environment influence on the T site properties and reactivity. It explains why
it may be difficult with mordenite to conduct highly reproducible pretreatments.
According to the experimental conditions various proportions of Al atoms can be
removed from the different Al sittings. Because of the presence of four topologically non equivalent T atoms MAS NMK does not give

yet

unambiguous and precise

Al population results, The only approach is still undirect through the changes
in properties.

L zeolite
This zeolite structure has two topologicallynon equivalent T atoms. They have high similarities in bond angles and bond distances which does not allow to
distinguish them easily for instance by MAS NMK. Consequentlytheirchemical properties should also be very close. Comparison with Y zeolite showed two similari-

56
ties. Firstly no Al extraction

from a specific

37 X of Al atoms weakly bonded

to the lattice were removed

HCl treatment

which also eliminates

cates again a correlation

the proton linked

T site was evidenced.

weak acidity

Secondly

in the beginning

of

[37,38]. This second point indi-

betweentheeaseofAlatom

removal and the strength

of

to them.

MFI

With twelve topologically

non equivalent

T sites for possible

Al location

by various amounts of Al04

in the second layer of
29
is a complex system.
Si MAS NMR did not yet resolve complete-

each of them being surrounded

tetrahedra,

MFI

ly the problem
explain

of the Al location.

the known difficulty

by different

DEPENDENCE
Chemical

samples

OF ACIDITY

tals,have

ON OVERALL

effects,which

been recognized

For example
structures

ENVIRONMENT

express

zeolite

the vOH wavenumbers

increases.

Si/Al ratio around

of zeolites

of acidic hydroxyls

(S int)for a series

equalization

principle

of zeolite

by Mortier

to

electronegativity

is decreased.

intermediate

The ca-

give a linear relaelectronegativity

of zeolites [43].
an average

their formula as T 0n (OH), in a manner

acid strength
comparable

of oxygens

fraction

It equals the potential

m=

shift of

[42]. This charge paral-

as the Al content

T is Si or Al, n the number

(m = Al/(Al+Si)).

0 and 0.5. In the oxyacids

as n increases

of zeolites

to oxyacids

not linked to protons

number

is to express

in solution

[44]. In zeolites

0, i.e. for a pure SiO2 structure.

[IO].

and m the Al molar

of protons

series, T On (OH), for instance,

from 0 to 3 and it is well accepted

OH group increases

applied

the intermediate

and n- decane hydrocracking

as a function

as

at Si/Al close to 10 [41].

charge of protons

in acid strength

Another way to calculate

1 and n varies

zeolite

shown that the chemical

also constant

partial

talytic conversions of isopropanol

tionship when plotted

in different

They decrease

allowed him to calculate

lels the known increase

bet-

porous crys-

with the Al content

-1
They reach a limit close to 3600-3605 cm
for a

electronegativity

and the average

in zeolite

chemistry.

6 [10,13]. It was recently

the field of zeolites

of long range interaction

properties

[10,39,40].

studied by MAS NMR becomes

The Sanderson

the influence

collective

to modify

lie on the same curve

the acid strength

when

Al environments

properties

The overall

between

potential

obtained separately or modified

procedures.

ween all atoms and which generate

protons

The very different

to compare

and varies

m equals

that the acid strength

of the

the limit value of n is 2

Consequently

n equals

2-m. The zeo-

57

lite formula T 02-m(OR), written for the theoretically pure protonic forms is
easily calculated. The 2-m values obtained for various zeolite types increase
with the experimental acid strength of the highly proton exchanged forms [lo].
They may be chosen as an evaluation of acid strength.
Similarities exist between the two types of calculation, Sanderson intermediate electronegativity (S int)and TO*_m(OH), formula. Both of them are based
only on the elemental analysis and then give a smooth correlationwithAlcontent
or any parsmaterrelated to it, for instance unit cell parameter or IR wavenumber
of TO bonds. None of them is able to evidence a change in acid strength not related to chemical composition such as the constancy observed below Si/Al close to
6 for OH wavenumbers. Figure 3 illustrates those points in showing the similarities between 2-m and S int values.
S&/Al

10

4.2

0.1

0.2

0.3

Al/Al + Si

Fig. 3. Change in Sanderson intermediate electronegativityS int. (a) and 2-m in

T02_m(OR)m formula (b) as a function of Al molar fraction m = Al/(Al + Si) in protonic zeolites.

Another parameter also changes smoothly with the zeolite Al content. The efficiency coefficient a0 defined in faujasites evaluates the apparent fraction of
a site effective in acid-base reaction as an activity coefficient does in solution. The o. value is the same for all the acid strengths considered. It does
not depend on the base used, cations present in zeolites or pretreatment temperature. It varies only with the Al content i.e. the charge density in the framework. As shown in Figi it increases from zero as the Al molar fraction decreases by dealumination of X andY samples

[Ill.

A value of 1 is considered as

the point where no interaction with close sites decreases the efficiency in catalysis. All the sites should have the same maximum efficiency. This occurs for an
Al molar fraction m =0.146 * 0.05 (%/Al = 5.8). It turns out that for Al contents lower than this value all the published results show a linear relationship

OS1"NNN

.J

Fig. 4. Dependence of efficiency coefficient ao as a function of Al molar fraction m = Al/CA1 f Si) in faujasites (from ref. 11).
between the catalytic activity in very different reactions and the Al level,
which is in line with a constant efficiency of sites [11,14,19,27-29,

Fig. 11.

The L and dealuminated L zeolites also showed the existence of efficiency coefficient depending again only on Al content [37].
The equation of the Y curve in Figure 4 is o. = -2.82 m 2 0.05 + 1.41.
The slope of the L curve is -2.47 f 0.05, slightly lower 1373. No such determinations could be performed for zeolites with smaller pores, too narrow for the large colored indicator

molecules.

All those results show that the acidity (strength and site efficiency) varies
smoothly with the zeolite composition. The hypothesis of overall effects and
their comparison with collective effects in solution appears to be a reliable approach.
Structural and chemical related properties
It was said above that the different topologies of faujasite and mordenite
lead to a different limit Al content below which all protons will be isolated
1251. In the scope of overall effects it is of interest to consider not only
next nearest neighbors but a larger number of tetrahedra involving an ensemble
of several layers of TO4 species. Using a topological concept based on coordination sequences, Meier and Moeck [16] consider all

the tetrahedra included between the

second and the fifth layer around a T site. Taking into account the non equivalent T sites, a weighted mean number of tetrahedra is defined and divided by the
maximum number of tetrahedra in a 4 - connected net of T atoms in the same ensemble of layers. This gives a topological density of T sites : TD2_5

[16,45]. The

values obtained are reproduced in Table I. They do not depend on unit cell, symmetry of the structure or chemical composition. Zeolites better used as catalysts and adsorbents lie between faujasite and MFI. The high value of mordenite
as said before, correlates with its 12 TO4 units in the second layer of
tetrahedra as opposed to 9 for faujasite.

59

Table I. Topological density TD2_5 (a)

Zeolite FAD
TD2_5

*181

LTA

RHO

.200 .200

LTL

OFF

ERI

.220 .222

.222

MA2

MEL

.248 -274

MOR

MFI

FER

BIK

.287 .306

.2?5 .278

(a) from [16,451

Aluminum topological density and acid strength

Since the acid strength is higher for far apart tetrahedra, the chance to have strong acidity for a given Si/Al ratio will change with the topological density. In order to combine chemical and topological approaches, an aluminum topological density TDAl can be defined using the Al molar fractionm :

TDAl = m

ID2 5

This factor evaluates the density of A104- in the ensemble of tetrahedra comprising the second to the fifth layer of (SiO4 f Al041 tetrahedra surrounding a T
site. It defines the Al molar fraction corrected for topological effects. As an
example numerical values are listed in Table II for some usual zeolites; their Si/Al

Table II. Evaluation of aluminium topological density and of acid strength

OFF

MOR

4
Si/Al
0.20
m (a)
TDAlx lil0(b) 4.44

4.8
0.17
4.68
3i.83

Zeolite

TDAl
2-m (c)
(d)
2-m

41D.8

RHO

LTL

ERI

2.4
0.27
4.86

3
0.25
5.0

3
0.25
5.5

3
0.25
5.55

3:.73

3i.75

3:'"

3i.75

X
1.2
0.45
8.14
1;'"

LTA
1
0.50
10.0
lt.5

(a) m = Al/Al + Si
(b) TDAl = Aluminium topological density
fc) 2-m = evaluates acid strength in TO2_m(OHfm
(d) 2-m/TDAl = proposed structural average acid strength

ratio is taken as in the synthesized form. They are ranked in an increasing order of TDAl which is of course different from that in Table I and which greatly
depends on the m value chosen. Figure 5 gives the changes in TDAl as a function
of m for the various zeolites. The slopes of the straight lines are the

TD2_5

values of Table I. Dashed lines are for regions where high Al contents are not
usual for the corresponding structure.

60

0.1

0.2

Fig. 5. Change

0.3

in aluminium

Al/Al + Si
topological

density TDAl as a function

of Al molar

fraction m = Al/Al + Si for:

1

: FER ; 2 : MFI, MOR ; 3 : MA2 ; 4 : LTL, OFF, ERI ; 5 : RHO, LTA ; 6 : FAU

Figure 5 allows several comments

the denser structures

to be made. At first it can be noted that

are not stable at high Al molar fractions

number of close Al-O bonds increases.

weak to exist in dense structures
ly about the parallelism
if dense structures

between

the strengthof

protons and that of Al-O bonds,

could exist at high Al contents,

the denser structures

the corresponding

due to their restricted

will tend to show mainly

will offer the possibility

replacement

i.e. for instance

of protons with very weak

for dealuminated

have the highest

chance to have close Al tetrahedra.

denite should favor bimolecular
mation as compared
least for mordenite.
formation

assuming

a perfect

like ferrierite
transfer

and mor-

and coke for-

This is in fact observed,at

the small size of the channels

to have Al tetrahedra

li-

density i.e. the highest

such as hydrogen

[46]. Inversely

Secondly

to be made at

that for a given Al content,

The denser structures

reactions

For ferrierite

observed.
structures

samples,

Al topological

to the less dense faujasite.

of coke precursors

the same chance

content

of the various

of Al by Si atoms. It shows for instance

the denser structures

protons

range of stability,

strong acid sites while the ligh-

of occurence

acid sites. This is in line with the trend experimentally

nes of Figure 5 allow an easy comparison
any Al content

i.e. when the

that the Al-O bonds are too

rich in Al. In view of what was said previous-

would be very weak. As a consequence,

ter structures

This suggests

prevents

the same Al topological

in a NNN locationoccurs

the

density, /i.e

at smaller Al

in the denser 'structures. This means that the chance to have weak acid

sites occurs at lower Al contents

ones. Thirdly
structure

information

in the denser

can be obtained

structures

than in the lighter

from Figure 5 as to the point for each

where none of the Al atoms will have an Al as a next nearest

neighbor.

61
At Al contents

lower than this limit expressed

as limit mRNN all the acid sites

should be strong.

Limit mgNN of next nearest

neighbor A10 - tetrahedra

4
were given above of m values in faujasite

Severalexamples

of the acid sites are strong. All those numbers

2i.e

m = 0.12 to 0.21

. In order to perform calculations,

the faujasite

structure

The one obtained

since it is very reproducible

talytic activity

23 and 40 Al/u.c.,

(Si/Al = 7.3 to 3.8). They could be used as references

to be chosen.

reaches

are between

below which most

from efficiency

a precise

coefficient

and is not disturbed

for

number has

a0 seems to be good

by any effect related

to ca-

measurement. As said previously and as it canbe seen frcnf@re

4, a0

a value of 1 at m = 0.146. At this point all the sites are supposed

be far apart enough

to

so that they do not interact with each other to decrease

their efficiency

and their acid strength. From Figure 5 the Al topological den-2

sity at mgNN = 0.146 is limit mRNN TDAl = 2.65 x 10 . Since TDAl integrates chemical and topological
TDAl is valid
values

obtained

lites. Values

effects

for any zeolite

from Figure

obtained

Table

limit mWNN

[25], considering

fraction

changes

MFI

MOR

MAZ

LTL
OFF
ERI

RHO

FAU

.092

.095

.096

.107

.120

.132

.146

9.9

9.5

9.4
.104

9.3

8.3

7.6

the limit WNNTDAl

the two types of evaluations

is similar

for the different

reach the limit Al concentration

hypothesis

te-

noted

Figure

being

the assumption

structures.

require

the curves

the only experimental.

hence,

calculated

that

As one might

a lower Al content

limit mWWN, at this point no AlO

with its neighbors,

6 reports

and HY

strengthens

zeolite

structures

6.8
0.136-0.166

below which all the sites are strong.

made to define

dra is in close interaction

for faujasite

proper-

of close A10

The very good agreement

: limit of no close protonic sites in H-mordenite

the structures.

in catalytic

fraction

zeo-

limit mWNN below which Al atoms should not

expect Table III shows that the denser

the

the limit mWNN

neighbor.

in Table III between

accepts

this hypothesis

and given in Table III for various

FER

limit Si/Al
limit
ref.(2*
ref. (25)

5 are evaluated

in HY and H mordenite.

III. Limit of Al molar

Zeolite

to think that the same limit of

Assuming

in Table III for the limit molar

a proton

have next nearest

structure.

by Wachter

ties, are also reported

trahedra bearing

it is reasonable

a0 should equal

to

If one
tetrahe1 for all

for oo changes with m, that

The calculated

slope for Ll'L

62
(2.64) is very close to the experimental one of 2.47 + 0.05 [14]. Both of those
values for L are lower than that of faujasite (2.82). Taking into account the
assumptionsmade the agreement can be considered as rather good.

C3
o

0.

I
2

0.1
f

0.2
1
1.8

Al/Al + Si
i.6

2-m

Fig. 6. a0 dependence on Al molar fraction m = Al/Al + Si or 2-m values for:

1 : FER ; 2 : MOR ; 3 : MAZ ; 4 : LTL, OFF, ERI ; 5 : RHO, LTA ; 6 : FAU

Structural acid strength

It was said that the Sanderson intermediate eleetronegativityor the 2-m value in TO2_m(OH)m can be used to evaluate the acid strength. Neither takes
into account structure effects. It is proposed to intrclducesuch influence
through the aluminum topological density. Since a high number of close Al next
nearest neighbors decreases the acid strength, the correction for structure effect
should decrease the average strength for topologicallydense and Al rich zeolites. Expressing the acid strength by 2-m for instance,a value corrected for
structure effect is 2-m/TDAl. The values obtained for the usual zeolite compositions are listed in Table II. They are in good agreement with the known range of
zeolite acidity. As compared to 2-m numbers alone they increase the difference
between weakly acidic zeolites (LTA,X) and the strongly acidic ones. No value is
calculated for the high silica zeolites (MFI for instance) since at those low Al
contents the acid strengths should be constant. At a given Al molar fraction (i.e.
given 2-m) the structural average acid strength should decrease as the topological density decreases. With the above hypothesis the highest acid strength rea-2
ched should equal for each structure Z-limit ~N/2.65 x 10
for m = limit ~~
According to Figure 5 this limit should be higher for the denser structures. More detailed calculations could be made but they would be too speculative in the
present state of the available experimental data basis.

63

CORRELATIONS

BETWEEN

It is worthwhile

EFFICIENCY

a0 and acid strength.

value and are supposed

coefficient

the Al topological

density,

which

cation,

on

and similarities

when the interaction

determines

that the acid strength

structure

a o characterizes

dehydroxylation,

topological

density

is very sensitive

H+/metal

strength

of the probe molecule

cation, valency

of cation,

of any of the above parameters,

that of ao, i.e. it increases

with Al content.

[lo]. By contrast
structure,
values

with what happens

the acid strength

strength

without

Changes
influence

of acid
to the

changing

insolution

intrinsic

vary

proper-

of the acid

in a given zeolite
not only cxo

but it also changes

the charge density.

is possible

limit

a0 and acid strength

on Al content modifies

anacid

since it affects

the a o coefficient

BETWEEN

EFFICIENCY

in catalytic
of efficiency

depends

in catalytic

COEFFICIENT,

activity

Modifying

only by exchanging

on the effective

activity

Two theoretical

una-

the

protons

number

can affect

AND CATALYTIC

should reflect

a0 and of acid strength

by

the simultaneous

since the rate of a

of sites and on their strength.

the volcano

ACTIVITY

curves expected

It will

for the change

with the Al level.

cases of catalytic

'W' requires

ACID STRENGTH

with Al content

coefficient

be shown how both factors

reaction

the behavior

zeolites

or by dehydroxylation.

CORRELATIONS

reaction

in solution,

do upon dilutionof

voidably

cations

protonic

as m decreases

lies in the zeolite

by acting

(i.e.
-

that when looking

are at the same time an acid and the solvent

the acid concentration

as it would

of protons

of highly

properties

The explanation

should also oc-

and to the

it. It follows

only the Al content

why two independent

density

dehydroxylation)

used to measure

with no modification

mNNN. One might wonder

and nature

or on the basici-

as for ao but it is well known

by changing

ties. Those materials

It was shown

acid sites as

the constancy

to th e actual

at the acid strength

similarly

effects.

protonic

on acid strength

[lo-121. For acid strength

exchange

parallels

with close sites

this point for the efficiency

[47] and that it did not depend on the content

cur for the same aluminum

effi-

, ---..z
i.e the density of charges and more precisely

to take into account

zeolite

ty of the probe molecule

strength

between

Both of them should reach their highest

constant

that this coefficient

well as metal cations

of metal

to become

The only parameter

is the Al content

experimentally

AND ACID STRENGTH

to point out the differences

ciency coefficient

is negligible.

COEFFICIENT

reactions

only weak acidity,

will be considered.

i.e. it will be catalyzed

The first
by all the

It may be for instance

acid sites, weak and strong, present

in a zeolite.

hol dehydration.

of type 'S' needs strong acidity.

The second reaction

not work with zeolite having

only weak sites.

It will only involve

alco-

It will

the strong

64
sites when they exist simultaneouslywith weak sites and finally all the acid
centers will catalyze the reaction when they are strong enough, i.e. when m <
limit mWWE. This may be the case of cracking reactions. For each of those two
limit cases 'W" and 'S' the influence of efficiency and acid strength are considered. The first parameter affects the "effective'number of sites and the second the turn-over number i.e. the 'energy'of sites or in other words AG involved in the elementary steps of the reaction.
Efficiency coefficient influence
The number of potential acid sites equals that of Al atoms i.e. is given by m.
For reactions of type 'W',assuming fully protonic zeolites, the effective number
of active protons is muo similarly to the case in solution where it is given by
IH"I aH+, IH+l and aH+ being respectively the proton concentration and its activity coefficient. The rate r of a reaction is proportional to m a . Figure
0

7A reports the change in this number calculated for faujasite with the limit
mWNN value of 0.146 used previously.Startingfrom high m values, the decrease in
m is compensated by the increasein a

up to 1 for mRRN = 0.146. Below this point

only the molar fraction m decreases. Curve a in fig. 7A shows a flat maximum
around 0.21 < m < 0.31 (3.8 > Si/Al > 2.2).
For type "S" reactions only the strong sites have to be considered. Experimental measurements of acidity and catalytic activity showed that in X and Y zeolites around 70 % of the acid sites are strong [5,14]. In addition below m = 0.146
all the acid centers are strong. Combining those experimental results with calculations of m a0 made for curve 7&a, gives curve 7 A-b for faujasites. The maximum of the volcano curve is clearly shifted to lower values for the strong acidi-

Si/Al 10

10

1.1, .

,*--.\
,

0.1

0.2

\.

0.3

0.4

0.1

0.2

0.3

Al/Al + Si

Fig. 7. Effective number of acid sites as a function of Al molar fraction m =

AllAl + Si. A

: faujasite, curve a : total acidity m a

dity higher than 88 I H2S04. B

LTL ; d : FAU.

curve b : strong aci-

: strong acidity for a : MFI ; b : MOR ; c :

65
ty case. It is situated close to 0.17 (Si/AlN 4.9) very similar to the experimental break observed in Figure

for isooctane cracking.

It was said previously that limit mNNN is shifted to low values for dense
structures. An attempt to compare the effective number of strong sites for various zeolite structures is given in Figure 7B. Experimental acidity measurements showed that approximately 60-65 % of the acid sites are strong (37) in L
zeolites. The limit

value is 0.12 from Table III. Those results allow

"NNN
curve c Fig. 7B to be proposed. Curve b Fig, 7B is calculated in a similar way
from ammonia heats of adsorption on mordenite which indicate that approximately
65 % of acid sites are strong and behave differently from the other 35 % [48].
For ME1 the limit mNNN is close to 0.095 (Si/Al = 9.5). This corresponds roughly
to the limit composition for the stability of the structure. It follows that for
this zeolite all the known materials are always on the left side of the volcano
curve, the maximum being not exceeded (curve a Fig. 7B).
A main conclusion from Figure 7 is that the maximum of the volacno curve of
effective strong acidity versus Al molar fraction shows a clear trend for a
shift to lower m values at high zeolites topological densities. Considering only
the Al molar fraction of different zeolites, but not any structure effect [49],
a broad maximum was observed between m = 0.09 and 0.18 for strong acidity evaluated by NH3 desorption between 673-873 K. The curve obtained

appears in fact

to be the envelope of those specific of each structure and depicted in Figure 7.

A second conclusion is the shift of the maximum abscissa to higher m values for
weak acidity.

Acid strength influence

Experimental studies of changes in catalytic activity with Al content show an
almost linear relationship for m < limit mNNN between activity and Al content
for faujasite [11,14,19,27-29,Fig. l] or ME1 [SO]. This implies that both cl0
and acid strength should be constant in this composition range.
The rate r of a reaction is given by

r = k INSIISI, k being the rate cons-

tant and INSI and ISI the concentration of active sites and of the substract.
The rate constant k is expressed by

k = KT/h exp AS"*/R exp -E/RT where ASof is

the standard entropy change at the transition state, E the apparent activation
energy and KT/h the universal frequency. The rate constant then involves the
acid strength which modifies E and AS",

a higher acid strength increasing the

turnover number. The approach described here shows how the change in catalytic
activity for m > limit mNNN depends on acid strength. Three parameters affecting
the strength have been pointed out. They are the limit mNNN value determining
the point below which all the sites should be strong, the correspondingmaximum
strength reached and the structural average acid strength. Firstly the limit

66
mRNN value should determine a break or a maximum asin curves of figure 7B. The
reaction rate shall increase almost linearly with Al content for m < limit mENN,
a range where acid strength is constant. It may decrease beyond this vaIue due to a

toweakeracidity not compensated by the increase in the number of sites. Secon-2

dly, the maximum acid strength 2-limit mNNN/2.b5 x 10
should be higher in den-

and

se structuressinceitis reached at lower limit mRNN. In the range m < limit mRNN
theacidstrengthraached
shmzldbehigherin denser structures. Thirdly as already said
the structural average acid strength 2-m/TDAl in the range m > limit mENN should
be lower in dense structures than in light ones for a given m Al molar fraction.

Combined a

and acid strength effect

Adding the influence on a reaction rate of the efficiency coefficient and of

the acid strength give many possibilities. In the absence of enough experimental
results no precise calculation can be made. In a tentative approach Figure 8

%/Al

IO

0.1

0.2

0.3

Al/Al + Si

Fig. 8. Estimated normalized rate of a reaction catalyzed by strong acid sites

as a function of Al molar fraction m = Al/Al + Si for a : MFI ; b : MOR ; c :
OFF : d : FAD.

gives an example of the sequence of the catalytic activity curves which can be
obtained for MFI, mordenite, offretite and faujasites in reactions involving
strong acidity. The ordinate maxima have been arbitrarily normalized at the same
value. The positions of the maxima abscissae are deduced from those calculated in
in Table III, the denser strucNNN
tures corresponding to the lower Al concentration at the maximum. For the usual
Figure 7B. Their order follows that of limit m

seolites one should have from Table III the following order for the abscissae of
the maxima :
FER < MFI < MOR < MA2 < LTLr\rOFF N ERI < LTA < FAD

67

For MFI the maximum

should not be reached

for usual Al contents

this type. This is in line with the experimentally

catalytic

activity

Experimental

studies

reported mainly
faujasites

with Al content

[4,19,51],

with m between

the maxima:

conditions

for mordenite,

and faujasite,m

agreement

3. The shifts

to slightly

type reaction
the maximum

which

comparison

'S' which

From the 33 topological

should give the maxima

fraction

OTHER FACTORS

reported

carbenium

ion chemistry.

tead of thinking
branched

activity

the hydrocarbons

consistent

way. More specifically

of various

zeolites

the cracking

n-octane

of n-paraffins

could be found if insratio and linear/

showed to vary in a

that ranking

the large number

formation

of C2 gave the

of C3 and the quite opposite

hydrocarbons.
sample.

order for

The ratios C2~C.4 or C3/C4 were

Table IV gives the order obtained

and n-decane.

in

to by their carbon num-

produced

in the order of increasing

production

(limit

at the hig-

on the only basis of classical

that a coherence

it was observed

each zeolite

of n-heptane,

as

SELECTIVITY.

in the cracking

formed are referred

of C4, C5 and higher

shown to characterize

'W'
7A

[16,45], bikitaite

at the lowest Al content

FIELD GRADIENT

ber. The sum of Cl, C2, C3, C4 .. . hydrocarbons

the formations

is a

from Figure

(Si/Al = 5.8)).

CATALYSIS.

It was observed

same order for the increased

of table

(respectively

hydration

shows this maximum

could not be explained

studied

numbers

As deduced

as usual only in terms of olefinlparaffin

products,

is in very good

by Meier and Moeck

faujasite

that the selectivity

of zeolites

order for

m = 0.14 (Si/Al =

should occur at higher Al molar fractions

densities

ACIDIC

vain the

require only strong acidity.

(limit mNNN = 0.146

It was shown recently

a large number

shows the following

by the fact that n-butene

of its catalytic

AFFECTING

for

[55] and bute-

three materials

than the limit ANN

iso-

isomeri-

of Figure 8 and limit mtiNN values

mNNN = 0.087 i.e. Si/Al = 10.5) while

hest molar

hydrolysis

made between

all the acid strengths.

rate for such reactions

to reactions

in the reac-

with the calculated

(Si/Al = 3.5 - 5)[53,56].which

values

is explained

For

[14,20], cyclopropane

(Si/Al = 8.7): offretite,

higher values

involves

of

have been

[53]. Lower values have been obtained

for butene hydration

= 0.22-0.17

0.096, 0.12 and 0.14b)

cracking

[54], ethylacetate

m = 0.10

with the calculated

of

0.2 and 0.11 (Si/

conditions

are in good agreement

8, A more detailed

same experimental

compared

isooctane

cracking

[56]. Those results

lues of Figure

reactions

of Al content.

0.11 to 0.04 (Si/Al 8 to 24) in the n-pentane

zation and n-andiso-octane

ne hydration

6)

and experimental

[52] and butene hydration

mordenite

in various

as a function

or a break at m values between

on the reactant

tions of cumene cracking

merization

activities

and mordenite

they show a maximum

Al 4 to 8) depending

of zeolites

linear dependence

[SO].

of catalytic

for faujasite

observed

This order does not depend

in
for

68

Table IV. C3/C4 ratios in the cracking

of n-heptane

and n-octane

at 723 K and n-

decane at 793 K (a).

n-C
MFI
ERI
H-OFF
H-K-OFF
MOR
HY
H NaX

33
3
4
4
4.8
2.4
1.2

1.22
1.7
0.96
0.83
0.86
0.8

(a) from ref.

[57-581

those various

structures

1.1
1.2
0.77
0.45
0.43
0.48

[57]. It was shown to increase

results

parameters

that the molecules

by the field and field gradient

density of charges

It is neither

between

structure

close charges

of n-paraffins

existing

highest

All those

are electronically

disturbed

which depend on the

in the space surrounding

which is the derivative

effect on molecules

very close to the charges

the charges

extents

In those circumstances

follow the classical

ions in a non disturbing

f3-scission rule based on the

environment.

take place at any C-C bond as in the scheme suggested

in solution

in MFI or faujasites

R1

R1

[60,61] which

was proposed

involves

to occur at various

H2
j-6 - R

v2
-

Rl-C.

_v*

,
k

- CH3 + +CH2 - R2

RI being H, CH3, C2H5 .. .

molecules

for the cracking

a pentacoordinated

[62,63]. It can be schematized

72 5
-C-C-R2+H+

of in-

of some C-C bonds.

that the attack of the proton on the disturbed

ion. Such a mechanism

will be pola-

the appearance

and with weakeningorstrengthening

would

of carbenium

in superacids

polarizing cations

molecules

on the cage type, with

are

between

there is not reason why the attack of a proton on such

hydrocarbons

It is proposed

the molecules

when the distance

of such field gradients,

depending

duced dipoles and multipoles

stability

pores where

and, for a given porosity,

Under the influence

rized to different

modified

in small and tortuous

the molecules.

0.1 nm in a cage

of the field should have the

increases -at low Al molarfraction- andwhenhighly

are present.

as the Al content

in the cavities

and on their location

to acid

increases.

It is known that the field gradient may greatly vary within

[59]. This field gradient

related

(pore size, pore length, aging)

for a given zeolite

[58] i.e. as the distance

suggest

3.1
2.3
1.68
1.27
1.39
1.3
1.07

on their Si/Al ratio.

strength nor to shape selectivity

decreases

n-c1o

2'

could

mechanism

carbonium

extents with f3-scission

as follows

This mechanism could be favored either by a very strong proton actingonanundisturbed C-C bond as described in superacids [60,62] or by a proton of an usual
strength attacking a C-C bond weakened by field gradient as proposed here. The
type of cage and consequently the geometry of the distribution of charges, number of charges and the polarizing power of lattice atoms are selectivity factors
of major importance.

CONCLUSION
The concept of aluminum topological density which integrates the influence
of chemical composition and of structure topology appears to be very helpful for
a better understanding of zeolite acidity. If it is assumed that the same limit
Al topological density should determine for any structure the limit Al concentration at which the A104- are not in a next nearest neighbor situation, the estimation can be made of the characteristic change in acidity and catalytic activity
depending on site

efficiency and acid strength. The good agreement observed for

four zeolites structures, MFI, MOR, OFF and FAU between experimental and estimated values strengthen the validity of the approach.
The selectivity in cracking reactions leading to the formation of light products < C3 is also structure dependent in the sense that it increases as the
charges in the space surrounding the molecules are closer to the reactant. It is
related to the field gradient created in the cages and channels.

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