CHAPTER-I

INTRODUCTION AND LITERATURE SURVEY

1
1.0 INTRODUCTION
The quality of life is strongly connected to a clean environment. The
environmental concerns and regulations have increased very much in the public and
in the governments all over the w(}r1d during the last two decades. Chemical industry
S
has been blamed for producing environmentally hazardous substances which cause
acid rain, a reduction in stratospheric ozone levels and so on. The awareness and
concern have given impulse for dc:veloping cleaner, more efficient and more selective
catalysts which play the most important role in chemical industry. Research and
development in catalysts are targeted to achieve "100% selectivity!" and "zero
emission!" The replacement of homogenous catalyzed processes having many well-
known drawbacks with heterogeneous ones is becoming more important in chemical
and life science industry.
1.1 HETEROGENEOUS CATALYSIS
There are only very few industrially important homogeneous catalytic processes
like (i) alkylations and acylations using Lewis acids such as AlCh and BF), (ii) the
W ACKER process, (iii) the OXO process and (iv) the MONSANTO process [1].
Nearly eighty percent of heavy industrial chemicals are obtained by heterogeneous
catalytic processes. Here the reactants and the catalysts are present in different phases.
Commonly the catalyst is a solid and the reactants are either gases or liquids. Rarely
the actual catalyst is a liquid at the reaction temperature, in which case, it must be
supported on a refractory solid.
A heterogeneous catalyst acts by providing an alternate reaction path with a
lower energy of activation. The general steps involved in heterogeneous catalysis are:
(i) diffusion of the reactants to the surface of the catalyst, (H) chemisorption of the
reactants on the surface, (iii) reaction at the surface, (iv) desorption of the products
from the surface and (v) diffusion of the products away from the catalyst. Of these,
chemisorption on the surface followed by reaction at the surface are the most important
steps. An effective catalyst must interact with the reactant(s) only just firmly enough to
cause chemisorption; strong chemisorption often "poisons" the catalyst.
2
Heterogeneous catalytic processes have many advantages over the
homogeneous ones. The main advantage is that it can be operated continuously In a
reactor without interruption. Being in different phases, the separation of the final
reaction mass from the catalyst is quite easy. The heterogeneous catalysts need be used
only in smaller amounts, are oftFn reusable, are more environmentally benign and
have little disposable problems in comparison with homogeneous catalysts.
Most of the solid catalysts are used in three major industries: chemical
processing, petroleum refining and pollution control. In terms of physical volume,
catalyst consumption continues to be dominated by petroleum refining. But cost-wise,
pollution abatement catalysts, being mostly made of costly platinum group metals,
match the cost of catalysts consumed in petroleum refining [2]. Every segment of the
catalyst business is growing and the world market for heterogeneous catalyst is
expected to reach highest peak in the coming years.
The properties of a good catalyst for industrial use may be divided into two
categories [3]:
(i) properties which determine directly catalytic activity and selectivity. Here
factors such as bulk and surface chemical composition, local
microstructure and phase composition are important.
(ii) properties which ensure their successful implementation in the catalytic
process. Here thermal and mechanical stability, porosity, shape and
dimension of catalyst particles enter.
Using a catalytic material in industry often reqUITes a compromise In the
properties of the catalysts to produce a material, which meets the contradictory
demands imposed by industrial processes. Experiments show that, in the majority of
cases, the chemical composition of the catalyst exerts a greater influence on its activity
than the method of preparation.
Heterogeneous catalysts are classified into several ways. Based on their
physico-chemical nature, they can be classified as follows:
3
(1) Metal oxides: Simple metal oxides, mixed metal oxides, supported metal
oxides and modified metal oxides.
(2)
(3)
(4)
(5)
Supported metalslbimetallic catalysts.
Zeoliteslmolecular si((.ves
.
Clays and
Solid supported heteropolyacids.
.
Reactions on surfaces may be classified in terms of reactant or product classes
or on the basis of mechanistic similarities [4]. The latter method is more suitable for
applying the principle of surface science studies and also for "designing" new
catalysts. The simplest classification is into two main groups:
(1) acid-base (ionic) reactions
Catalytic cracking, hydration, dehydration, hydrolysis, isomerisation and a
host of other reactions pertain to this type. Acid-base property of a
heterogeneous surface is the important factor in determining the catalytic
efficiencies for these types of reactions. In acid-catalysed reactions,
reactants act as bases toward catalysts which act as acids and in base-
catalysed reactions, vice-versa.
(2) Oxidation-reduction (electronic) reactions:
Reactions pertaining to this type are those of oxidation, reduction,
hydrogenation, dehydrogenation, decomposition of unstable oxygen
containing compounds and others. The reactions are catalysed by solid
possessing free or easily excited electrons i.e. metals and semiconductors.
Metal catalysts can be supported or unsupported and are primarily used for
hydrogenations, isomerisations and oxidative dehydrogenations. Semiconductor oxides
are most commonly used in oxidations. These are materials in which the metallic
species is relatively easily cycled between two valence states and are exemplified by
the transition metal oxides. These are simple or complex oxides which can act as acids
or bases as well as redox catalysts.
4
1.1.1 Solid acid-base concept in heterogeneous catalysis.
Tanabe [5] defined a solid Jicid as one on which the colour of a basic indicator
changes concomitant with its cherhisoprtion. Following both the Br,pt1sted and Lewis
definitions, a solid acid shows a tendency to donate a proton or to accept an electron
pair, whereas a solid base tends t<,> accept a proton or to donate an electron pair. An
.
exhaustive list of various solid acids and bases is tabulated by Tanabe [5]. This list of
solid acids includes various naturally occurring clay minerals, zeolites, the well- known
solid acid namely silica-alumina, various metal oxides, sulphides, sulphates, phosphates
and halides. A list of solid superacids i.e. acids stronger than 100% sulphuric acid or
having the Hammett acidity function, Ho less than -11.9, is also given. This includes
Nafion, ZSM - 5 zeolite and sulphate-modified zirconia, titania and ferric oxide.
However, the classification of solids into solid acids and solid bases may, in several
cases, not be meaningful due to large heterogeneity of solid surfaces. The best example
is alumina which is a typical amphoter.
A complete description of acidic and basic properties on solid surfaces requires
the determination of the number, strength, type and distribution of the acid and base
sites. The exposed cations and anions on oxide surface have long been described as
acid-base pair sites.
Several acidic properties originate from local surface defects. Thus the exposed
metal cations which are coordinatively unsaturated (CUS) act as Lewis acid sites
accepting electrons from adsorbed molecules. The strength of these acid sites depends
on the charge and size of the cations. By the hard-soft acid-base (HSAB) concept,
cations of higher charge to radius r ~ t i o are harder. Surface hydroxyl groups originating
from incomplete dehydration exhibit considerable Br,pt1sted acidity. Electron deficient
states are also formed by the introduction of foreign cations into the lattice of a solid,
which, due to different co-ordination number, are not able to compensate for their
positive charge. The stronger acidity of mixed oxides over the single oxides is due to
such charge imbalances. Acidic properties can also originate from chemical
5
modifications of a surface like introducing a ligand having a different electronegativity
than the lattice anions [6].
Adsorbed Bq6nsted acids often dissociate on an oxide surface causing
?
protonation of the surface oxygerl anions and coordination of the conjugate base of the
acid to surface cations. This reaction is schematically depicted as
,
R H
R-H + M- 0----. M-O
The key requirement for such a dissociation of reactants is one of coordination
vacancies on the surface metal cations (Lewis acid sites) and surface B r ~ s t e d basic
sites to abstract and to bind the protons originating from the adsorbate. Experimental
evidence suggests that the presence of coordinatively unsaturated (CUS) metal cation
rather than CUS-type oxide ion is decisive in such adsorption. Steric arguments also
justify this. The smaller neighbouring cations in the lattice may obstruct access to
oxide ions less than the larger anions obstruct the cations. Again, the small - sized
proton has to bind to the relatively unobstructed oxide anion while the bulky organic
conjugate base anion must bind to the more hindered surface metal ion. Small wonder
that the co-ordination environment of the surface cation is the critical surface
characteristic [4].
Heterogeneous acid catalysis attracted much attention primarily because of its
involvement in petroleum refinery. Solid acid catalysts are invariably used in the
petroleum cracking process which is the largest among the industrial chemical
processes. Extensive studies unde,rtaken in the 1950s revealed that the essential nature
of cracking catalysts are acidic. Generation of acidic sites on the solids was
extensively studied. As a result, amorphous silica-alumina was utilised as a cracking
catalyst for a long time. Presently zeolites (crystalline alumino silicates) have replaced
almost all other kinds of catalysts in cracking.
6
In contrast to these extensive studies on heterogeneous acidic catalysts, fewer
efforts have been given to the study of heterogeneous basic catalysts. The first study of
heterogeneous basic catalysts, that sodium metal dispersed on alumina acted as
effective catalyst for double bond migration of alkenes, was reported by Pines et al. [7].
i
The various types of heterogeneous basic catalysts are [8]:
(1) Single component metal oxides: - oxides of alkali, alkaline earth and rare
earth metals, Th02, zr02, ZnO and Ti02 .
.
(2) Zeolites:- alkali ion- exchanged and alkali ion- added zeolites.
(3) Supported alkali metal ions: - alkali metal ions supported on a l u m i n ~
silica or alkaline earth oxide.
(4) Clay minerals:- hydrotalcite, chrysotite, sepiolite.
(5) Non-oxides:- KF supported on alumina, lanthanide imide and nitride on
zeolite.
Except for non-oxide catalysts, the basic sites are believed to be surface oxygen
atoms. These oxygen atoms would be able to interact attractively with a proton.
Some important solid base catalysed reactions are: double bond migration
reactions of unsaturated compounds, alcohol dehydrogenation to aldehydes or ketones,
. hydrogenation of olefins, amination of conjugated dienes, Meerwein - Ponndorf -
VerIey (MPV) reduction, side chain alkylation of aromatics, aldol condensation etc. etc.
1.1.2 Methods of Preparation
The goal of a catalyst manufacturer is to produce and reproduce a commercial
product which can be used as a stable, active and selective catalyst. Subtle changes in
the preparative details may result in dramatic alteration in the properties of the final
catalyst. In spite of numerous studies, the preparation of heterogeneous catalysts with
specific properties is still regarded as an art, often kept as a secret by the catalyst
manufacturer. However, many preparative routes are sought so as to give catalysts
with sufficient surface area, good porosity and suitable mechanical strength.
Schwarz et al. [3] divide the preparation of almost all catalysts into two main
routes: (i) methods in which the catalytically active phase,is generated as a new solid
phase by either precipitation or a decomposition reaction. This involves 'blending" of
7
proper reagents from a liquid or solid medium and (ii) methods in which the active
phase is introduced and fixed onto a pre-existing solid by suitable impregnation
methods. This involves "mounting" of the catalytically active material on a pre-
existing support.
~
S
Between these extremes lie methods which are best characterised as solid
transformations and includes dispersion of metals into thin films or colloids. Along the
"blending" route, the most oommon preparation methods are precipitation, co-
precipitation, gelation, complexation, crystallization and ceramic methods.
The most common method for preparation of bulk oxide catalysts is the
(co)precipitation of a precursor phase, usually hydroxides or carbonates, followed by
filtration, washing and calcination of the product leading to the oxidic phase. The
creation of the precursor solid phase from the liquid medium results from two
elementary processes which occur simultaneously or sequentially: (1) nucleation i.e.,
formation of the smallest elementary particles of the new phase (2) growth or
agglomeration of the particles. Factors such as pH, temperature, presence of impurities,
nature of reagents etc. are important in determining the morphology, texture and the
structure of the precipitates, e.g., under conditions of super-saturation, the rate of
nucleation is much faster than rate of crystal growth and leads to numerous yet very
small particles. The chemical and physical properties of particles kept in contact with
the mother liquor may change due to secondary processes. This <aging' or 'ripening'
leads to an increase in particle size of precipitates and agglomeration of colloidal
particles. A better method of mixing the components is achieved by the continuous
homogeneous precipitation where the precipitating agent, usually Olf ions, is slowly
and continuously generated by a controlled hydrolysis process such as hydrolysis of
urea.
The co-precipitation method used to synthesize multi-component systems does
not often give homogeneous precipitates due to differences in the solubility between the
components. Under conditions of slow precipitation rate or poor mixing, co-
precipitation is selective and the coprecipitate is heterogeneous in composition.
8
A more unifonn precipitate is obtained if the metal solution is quickly added to the base
with continuous stirring.
In contrast to the (co )precjpitation route, the sol-gel method (gelation) is a
homogeneous process which results in a continuous transformation of a solution into a
hydrated solid precursor (hydrogel). Sol-gel methods allow the control of texture,
composition and homogeneity ofth,e finished solids. The nanoscale chemistry involved

in sol-gel method is a straightforward way to prepare highly divided materials. The
method involves the hydrolysis and gelling (by the controlled addition of water) of
metal alkoxides or other reactive compounds in alcoholic solutions. The resulting open
structure in which the primary units are held together by chemical or dipole forces is
imbibed by the solvent. This structure is transformed to the solid phase by high-
pressure heating whereby the liquid contained in the gel changes to supercritical
vapours. Drying this under supercritical conditions gives aerogels where the solid does
not collapse and retains the open structure. These aerogels have high porosity, large
surface area, extremely low thermal conductivity and very good textural and structural
stability.
Crystallisation has found wide applications in the preparation of homogeneous
microporous crystalline solids in which the active phase is distributed uniformly. Such
materials are designated as molecular sieves and includes the various zeolites
(crystalline aluminosilicates), ALPOs (aluminophosphates) etc. A typical zeolite
synthesis involves mixing together alkali, sources of alumina and silica, water and other
components in appropriate proportions. The resulting gel is subjected to elevated
temperatures in autoClaves for crystallisation, which usually occurs in a time span of
several hours to weeks. Zeolite synthesis is, more or less, an art.
The complexation method makes use of chemical reactions which transform
slowly and without physical discontinuity the homogeneous solution of catalyst
precursors into a homogeneous, amorphous phase with either glassy, jelly-like or
foamy appearance. This precursor is then dried and decomposed to yield better
intermixed and more highly dispersed oxides than those prepared by the usual
precipitation route. To obtain smooth gelation, the catalyst precursors are complexed
9
or chelated with multifunctional organic reagents, yielding three-dimensional organic
network with the metallic component entrapped in this structure. Metallic elements are
added as water-soluble salts and various a-hydroxy acids ( e.g. citric acid) are used as
complexing agents.
In the high temperature ceramic method, the mixed oxide phase results from
heating intimately mixed powders at temperatures high enough to allow interdiffusion
and solid state reactions. Precutsor compounds, such as carbonates and oxalates, that
decompose at lower temperature, have also been used instead of the corresponding
oxides. This method has the advantage of the extreme simplicity and its use is essential
for preparing single phase mixed oxides such as perovskites and spinels. A major
shortcoming of the ceramic method is the lack of homogeneity of the materials
prepared because the solid state reactions between the precursor oxides occur with very
slow rates. Again, the high temperature (about 1300 K) required to complete solid
state reactions leads to drastic decrease in surface area of the resulting material by
sintering.
1.1.3 Transition metal oxides as catalysts
Not only do the transition metals themselves possess high catalytic activity, but
also do their alloys and compounds with non-metals like oxides, sulphides etc.
Generally transition metal oxides are active catalysts for oxidation-reduction processes.
But these systems also exhibit acido-basic properties, being capable of soprtion of acids
and/or bases as well as of catalysing some acidic reactions such as dehydration of
alcohols, isomerisation of hydrocarbons etc. Usually transition metal oxides are
components in catalysts used for reactions such as oxidation, oxidative and non-
oxidative dehydrogenation, reduction, ammoxidation, metathesis (production of long
chain alkenes) and water gas shift reaction (production of hydrogen). The variable
valence of the constituent metal ions enables the oxide to act as a sort of "electron
bank." Much work was done by the research group at the Ford Motor Co. (USA) upon
chemisorption of CO2, CO and NO probes on the first row transition metals oxide
catalysts within the framework of NO plus CO removal from the exhaust gases of car
engines [9]. Again, much work was devoted to the semiconductor aspects of these
systems and to the interpretation of simple reactions in terms of the boundary-layer
10
theory or similar concepts [10]. Many transition metal oxides have n-type or p -type
semiconductor properties. On heating in air, n-type oxides lose oxygen. The loss of
oxygen by an n-type oxide is made possible by the availability of a lower oxidation
state of the metal ion as in TiO:z. V'J/)s, crO), CuO or Fe:z03. The adsorption of oxygen
onto a p-type oxide is made possible by the availability of a higher oxidation state for
the cation as in CU:zO, Cr:z03, CoO and NiO [11]. The adsorbed oxygen on a p-type
oxide is more active than the l a t t i c ~ oxygen of an n-type oxide. Hence' n-type oxides
,
are used for selective oxidation of hydrocarbons, as oxidation on p-type oxides often
gives only carbon dioxide and water.
Often transition metal oxides act as a precursor for other catalysts. An example
is the doping of molybedenum sulphide with cobalt (II) oxide on an alumina support to
make a commercial hydrodesulphurisation (lIDS) catalyst [12].
Transition metal oxides also have acid-base properties. Auroux et al. [13]
studied the adsoprtion of ammonia and carbon dioxide on various oxides
microcalorimetrically and concluded that transition metal oxides are either acidic (A-
type) or amphoteric (A-B type). Numerous works were done to correlate the acid-base
properties of mixed transition metal oxides with the catalytic activity/selectivity in
selective oxidation of hydrocarbons [14-17]. In spite of numerous works no general
correlation between acido-basic properties and performance in oxidation reaction has
been so far formulated [18].
Titania and zirconia have attracted much attention because these are good
supports for metal catalysts and also change to superacids on combining with a small
amount of sulphate. TiO:z is classed as weakly acidic while zrO:z as acid-base
bifunctional [5]. V
2
0
S
, Nb:zO
s
and,Ta:zOs are typical solid acid catalysts. Oxides of
Cr, Mo and W are seldom used as single oxides but are used as mixed oxides with
alumina and silica for dehydrogenation, hydrogenation and skeletal isomerisation of
hydrocarbons.
Ferric oxide is regarded as weakly acidic and basic and is practically used for
oxidation or dehydrogenation reactions as single oxides promoted by alkalies or as
11
mixed oxides. Typical examples are dehydrogenation of ethylbenzene (Fe203-K),
water gas shift reaction (Fe203-Cr203), ammoxidation of propylene and
dehydrogenation of methanol(Fe203-Mo03) [19 a]. Tanabe [19 b] found that Fe203
prepared from ferric alum is very acidic and active for several reactions. Again Fe203
obtained by heat-treating of Fesb4 showed maximum acidity and catalytic activity at
the calcination temperature of 700C for several reactions [20-24].
CoO and C0304 are the drdinary oxides of cobalt and C0
3
04 is one of the most
active single metal oxides for oxidation reaction [5].
Non-stoichiometric nickel oxide has high catalytic activity for deep oxidation.
NiD mixed with solid acids such as Si0
2
[25], Si0
2
-Ah03 [26] and NiS0
4
[27] are
active for dimerisation of olefms.
Copper oxides CuD and CU20 are semiconductors and effective for redox-type
reactions such as oxidation or dehydrogenation. Many copper-based catalysts such as
CuD-ZnO [28], Cu-ZnO-Ah03 [29] and [30] have been reported to be
effective for dehydrogenation of cyclohexanol to cyclohexanone.
Transition metal oxides as binary or ternary complex oxides with definite
crystal structure show greater structural stability and catalytic activity. Thus single
phase complex oxides of fonnula AB03 having the perovskite structure and the
general formula AB204 having the spinel structure have been widely studied for their
surface properties and catalytic activities. In the present investigation , iron based
spine! oxides of cobalt, nickel and copper are chosen.
1.1.4 Sulphate-modified oxides as catalysts
It is well-known that surface modification of metal oxides with anions,
especially _ sulphate ions, often enhances their acidities and catalytic activities.
Sulphation of metal oxides has been most widely studied because some of these are
found to be superacidic. The discovery of solid superacids free of halogens can be
traced to the study of the effect of anions on the preparation of Ti0
2
[31]. Further
studies, especially by the researchers of Hokkaido University, reveal that, among the
12
various sulphate modified oxides, only sulphated zr0
2
, TiO
z
, HIDz and Fe
Z
03 or their
binary mixtures and metal promoted sulphated zrOz showed superacidity [32].
Superacids are important catalysts for skeletal isomerisation of n-alkanes and
alkylation of aliphatics by otefins to produce high octane gasoline components in

petroleum industry. Researchers hive long been seeking to replace liquid superacids
with less corrosive solid superacids and hence there is a great interest in the study of
sulphate modified oxides. More than 200 papers and patents on solid superacids
(mainly, soi-;zrO
z
and its mbdified ones) have been reported since 1990.
Nevertheless, not many industrial processes have yet been developed using sulphated
metal oxides as catalysts mainly due to catalyst deactivation and low selectivity caused
by the strong acidity [33].
The standard procedure of sulphation is the impregnation of the metallic
hydroxide or oxide by soaking these with a definite amount of IN H
1
S0
4
or dilute
ammonium sulphate solution for a few hours followed by filtration (without washing ),
drying and calcination. Instead of filtration evaporation of the solvent to get a dried
mass, followed by calcination is also adopted [34]. Generally ( not always), sulphation
increases the surface area of the catalyst. This is attributed to the inhibition of sintering
and the delay in the transition from amorphous to crystalline phase during calcination
[32,35].
Many theories are put forward to explain superacidity, but the exact nature of
surface acidity in sulphate-modified oxides remains controversial [36]. Some authors
[37,38] report that sulphated zirconia has strong Lewis acidity arising from
coordinatively unsaturated Zr
4
+ centres, whose positive charge is enhanced by the
inductive effect of the neighbouring S = 0 groups. Some other authors [39,40] report
the co-presence of both Lewis (cationic) and (protonic) acidities responsible
for the peculiar catalytic features of sulphate-doped zrO
z
. NMR study of acid sites on
sulphated zirconia using trimethylphosphine as a probe, supports the latter view [41].
IR studies of adsorbed pyridine show the presence of both Lewis and sites on
sulphated oxides. The nature of acid sites (Lewis or on sulphated zirconia
depends critically on the water content , which, in turn, depends on the history of
pretreatment of the sample. The water content of a working catalyst can also be
affected by moisture present in feedstocks and by water produced during the reaction
[42].
13
The following models ,1 - V, are proposed for the structure of surface sulphate
on sulphate-modified zirconia.(Fig. 1.1.1)
o
11
s
/1"
o 0 0
Zr Zr Zr
I
n ID
H
IV
v
Fig. 1.1.1. Various models proposed for sulphate-modified zirconia.
Model I and II are proposed by Tanabe and coworkers [32,35] for the sulphate
modified zirconia in the absence of and in the presence of moisture respectively.
Models ill, IV and V are proposed by Lavalley and co workers [38,43,44] for the same
catalyst. Model ill corresponds to low sulphate loading, IV to high sulphate loading
and V to low sulphate loading in presence of moisture. In model V, it appears as if
Zr02 is modified by bisulphate sp,ecies (HS04 j. In fact, the existence of HSO,, on
sulphated zirconia has been proved both experimentally [45] and theoretically [46].
The presence of superacidity may be tested by the catalytic activity for low
temperature isomerisation of n-butane to isobutane reaction, which is catalysed only
by superacids. Again, IR spectra of superacidic sulphated oxides typically give a
14
single strong band near 1380 cm-I, in addition to a number of weak bands in the range,
900-1100 cm-I [38].
SUlphated oxides are also found to be effective for acylation reactions [47-50].
These are also potential catalysts fOi hydrocracking of hydrocarbon polymer wastes to
i
C
4
- C
2
0 liquids with gasoline components exceeding 75% [51]. The surface electron-
donor properties and catalytic activities of sulphate modified zirconia [52], samaria
[53] and stannic oxide [54] have also been investigated.
,
Since SOl-lFe203 has superacidic properties and the present work involves
investigation of spinel ferrites of Co, Ni and Cll, we took it as an interesting extension
work to study the effect of sulphation on these ferrospinels. Literature survey reveals
that sulphation studies of spinel-type mixed oxide catalysts have not been so far
attempted.
1.2 SPINEL STRUCTURE
Spinels fonn a large class of compounds whose crystal structure is related to
that of the mineral spinel itself, MgAh04. The general formula of spinels is AB
2
0
4

The structure can be described in terms of cubic close packing (ccp) of the anions,
bound together by suitably placed interstitial cations. Most of the spinels are oxides,
some are sulphides, selenides or tellurides and a few are halides. Again the charge
distribution of cations can be 2-3 as in MgA}z04, 2-4 as in M ~ T i 0 4 and 1-6 as in
Na2W04 [55]. Of these, 2-3 oxidic spinels are the commercially most important.
The unit cell of spinel structure consists of 8 formula units and hence is
represented as AgB
I6
0n. The space group of a spinel is Fd3m. The ccp of 32 oxygen
anions will have 64 tetrahedral (T) voids and 32 octahedral (0) voids. Of these, only 8
T-voids and 16 O-voids are occupied by cations in an ordered way. These are called
A-sites and B-sites because A cations occupy T -sites and B cations, O-sites. The unit
cell of spine! structure is shown in Fig 1.2.1. Here the structure is shown in such a way
that the A cations fonn a supercage fcc unit cell. The cube is divided into 8 octants.
The structure within the octants can be imagined as containing A0
4
and B
4
0
4
structural
units in alternate octants [56]. Fig.1.2.2 shows the arrangement of A0
4
and B
4
0
4
units
in two neighbouring octants in the unit cell. The atoms are in three sets of special
15
positions and some typical fractional coordinates of the atoms are (0,0,0) for ~
( 5/8,5/8,5/8 ) for B and (3/8,3/8,3/8) for oxygen. The location of oxygen is an
adjustable parameter in the spinal structure and is called the oxygen parameter, u. It
has a value 0.375 in the ideal structure. This parameter characterises the difference in
the expansion of tetrahedral ruf1 octrahedral sites in order to accommodate larger
cations. In the ideal ccp structure of oxide ions, T -sites can accommodate cations with
radii ~ 0 . 3 0 AO and the O-sites, cations with radii ~ 0.55 AO [57]. But the cations in the
spinels are usually larger than these and hence the T - and O-sites have to expand in the
[111] direction (Le. along the body diagonals of the unit cell) to accommodate the
cations. If the expansion of T- and 0- sites occurs in the same ratio, u is still 0.375.
But usually T-sites expand to a larger extent than the O-sites to produce a non-ideal
structure having u> 0.375.
Fig 1.2.3 represents the immediate neighbours of an anion ill the spinel
structure. Each anion is surrounded by one A and three B cations. If' a' denotes the
unit cell edge length, the AX distance is a(u-Y4).y3, the BX distance is a(5/8 - u), the
angle AXB is 125 and the angle BXB is 90, for small deviations from the ideal
structure. This means that the BB distance .y2a14 is considerably shorter than the AA
distance .y3a14. As u equals 3/8 for the ideal spine1 structure ,we get AX distance as
.y3a18 and BX distance, al4 [58]
1.2.1 Normal and inverse spinels
The spinel is called "normal" if A cations occupy T -sites and B cations, 0-
sites. But Barth and Posenjak [59] pointed out a second possibility in which half of
the B cations occupy the T-sites and all the A cations together with the other half of
the B cations occupy the O-sites. When this is the cation distribution, it is known as an
inverse spinel. In between these extreams, it is possible to have various degrees of
randomization where both types of sites are occupied partly by A cations and partly by
B cations. These are known as random spinels. (Table 1.2.1). The cation distribution
may be described by a parameter A, defined as the fraction ofB atoms in T-sites. For
a normal spinel A = 0, for an inverse spinel A = 0.5 and for a completely random spinel,
A = 113 [60].
Fig. 1.2.1. The unit cell ofan ideal spinel structure. Hatched circles indicate A cations,
unhatched circles indicate B cations and large unhatched circles indicate oxygen anions .
..... "'>- -- - - - ------;/1
"' ..... I ..... I ",'" I
--;--- ,
I ..... I I
I I
I I
I I
1 I

" I
p
..... I' "'..... I
---1---- -- I I
I I l / I I I
I I I '- I I I I
I . 1 I I I I I. I
I
I .".-:' I I.".'" I I ..... "'''
I -- V-___ .L ___
I"" I ...... '" ,I ............
....... I . I .... 1::"' ________ _______ _ j ....
1140
.. ..
.. 1""----: .. ',
-1----( I
I I I
I I I
I I I
I I
I __ J
"
.. "1""---- B
I ,-'
1"'---,----,- I
I I I
I I t I
I I I I
I } A I I
I
.,,:,, .,./
...
FIG. 1.2.2 Unit cell of the ideal spinel structure FIG. 1.2.3 The nearest neighbours of
The position of the ions in only two octants shown. anion in the spinel structure. X:
The dashed circles belong to other octants. A: A-SITE CATION; B: B-SITE
Large circles: ANIONS; small hatched circles: B-SITE a: cell edge.
CATIONS; small unhatched circles: A-SITE CATIONS.
17
Table 1.2.1. Examples of some normal and inverse spinels.
Type Structure Examples
Normal (A) Tet [Bz] Oct 0 4 ZnFez04. MgCr204
Inverse lE) Tet [AB] Oct 04 NiFe204. CoFe204
t
Random (0< x< 1) (AxBI.x) Tet [AI.x Bl+x]Oct 04 ~ e Z 0 4 . FeMnz0 4
1.2.2 Individual site preference of some cations
The distribution of cations in the available T - and O-holes depends on a
number of factors of which the following are important.
(i) Cation size
A greater stability on the lattice is expected if the smaller B cation occupies the
smaller T -site. Thus, if the .radius of B cation that. of A. cation,. the. tendency is
towards inverse spine!. But the polarisation effect often outweighs this. Large AZ+
ions have less polarising influence on oxide ions than the small B
3
+ ions and hence
B
3
+ ions in octahedral sites stabilise the structure due to this higher degree of
po1arisation, favouring normal spinel structure [61].
(ii) Madelung constant
Taking chemical bonding in spinels as purely ionic, the main part of the lattice
energy is contributed by the Coulomb energy and Born repulsive energy. The
Madelung constant (M) of the, spine! structure has been calculated by Verwey, De Boer
and Van Santen [62] as a function of the oxygen parameter u and the charge
distribution among the A- and B- sites. Their results are represented in Fig. 1.2.4
where M is plotted as a function ofu for different values of the average ionic charge on
A-sites ,qA. From this figure it is clear that, for electrostatic reasons, it is favourable to
have either large ions (high u) with low charge or small ions (low u) with high charge
on A - sites. The Madelung constant of inverse 2-3 spinel is hardly affected by the
oxygen parameter.
The second energy term is Born repulsion. It is difficult to take this energy term
into account due to lack of compressibility data. But, on geometric considerations, it is
18
concluded that, in normal spinels, the relatively small tripositive ions on B-sites cause
anion-anion contact, resulting in a less favourable stacking and a larger edge length.
The unit cell edges ofnonnal2-3 spinels are about 0.8% [63] larger than those of the
corresponding inverse spinels.

0.375
0.381 0.387

Fig. 1.2.4 The Medulung constant M ( in e
2
/a units ) of the spinel structure as a
function of the oxygen parameter u for different values of the average ionic charge on
A sites,qA
Dunitz and Orgel [64] and simultaneously McClare [65] have calculated site
preference energies of transition metal ions in oxides using crystal field theory (CFT).
19
The crystal field stabilisation energies (CFSE) are given in units of Aa and L\t in Table
1.2.2 and in the units kJ mort in Table 1.2.3 respectively, for various d-electron
configurations [ 66].
~
Table 1.2.2 Crystal Field Stabilisation Energies calculated for different 'd'.
systems
.
Crystal Field Stabilisation Energy
Configuration
Octahedral field Tetrahedral field
d
l
and d 6
0.4 ~ 0 0.6 ~ t
d
Z
and d 7
0.8 ~ 0 1.2 ~ t
d
3
and d 11
1.2 ~ 0 0.8 ~ t
d
4
and d Y
0 . 6 ~ 0 0 . 4 ~ t
d ~ and d lU
0 0
Table 1.2.3 Crystal Field Stabilisation Energies (kJ mor1)estimated for transition
metal oxides, from spectroscopic values of 0 and ~ t (Data from Dunitz and
Orgel)
Ion Octahedral Tetrahedral Excess Octahedral
stabilization stabilization stabilization
Te+
d
l
87.4 58.5 28.9
V
j
+
d
l
160.1 106.6 53.5
Cr
j
+
d
j
224.5 66.9 157.6
Mn
3
+
d
4
135.4 40.1 95.3
Fe
3
+,Mn
1
+
d:>
0 0 0
Fe
l
+ dO
49.7 33.0 16.7
Co
z
+
d
7
92.8 61.9 30.9
Nfz+
d
ll
122.1 35.9 86.2
Cu
l
+ d'l
90.3 26.8 63.5
20
These data show that d
5
and d
lo
configurations have no site preference while d
3
and dB have very large octahedral site preference. Ions with d
4
and d
9
configuration can
be stabilised additionally by Jahn-Teller distortions. If the regular Oh symmetry
octahedra of surrounding anions is elongated or compressed in the c direction to give
~
D4h symmetry, the doublet (eg) aid triplet (t2g) levels split. The splitting of the doublet
is larger. It is clear that, in the case of elongation, the d
z2
orbital is stabilised compared
to the d
x2
y2 orbital. So metal ions with d
4
and d
9
configuration have an extra
stabilisation equal to half the splitting of the doublet. Fe[CuFe]04 and Zn[Mnll04 are
examples of tetragonally distorted spine Is with cia> 1 (c and a are the unit cell edges
along the z and x directions).
Partial covalent bonding using hybrid orbitals can influence site preference of
cations. d 10 ions show a marked tetrahedral site preference as they can use Sp3 orbitals
to form covalent bonds with the p-orbital of oxide ion. Examples are Zn
2
+ and Cd
2
+
ions. ZnFe
2
04 and CdFe204 are the only known normal ferrospinels.
Blasse [67] derived site preference of cations on the basis of the Molecular
Orbital Theory (equivalent to the Ligand Field Theory) which takes into account both
covalency and crystal field stabilisation energy simultaneously. According to Blasse's
approach, d
3
ions have the strongest O-site preference while d
5
, d
6
d
7
,d
9
, or dIG ions
prefer T-sites. dO,d
1
,d
2
,d
4
and dB ions do not show any pronounced site preference.
When the various factors as mentioned above are counterbalancing there can be
a completely random arrangement of metal ions among the eight T -sites and sixteen 0-
sites.
1.2.3 Ferrospinels
Spinel oxides containing iron are called ferrospinels. The interesting electrical
and magnetic properties of these compounds are governed critically by their chemical
composition. Hence preparation of ferrite composites, with specific properties has
gained much importance. Simple ferrospinels (AIIFe204) as well as mixed ferrospinels
(A
Il
t

x
BIlx Fe204) are known..
21
1.2.4 Magnetic and Electrical properties of ferrites
Historically ferrites attracted the attention of physicists and technologists since
they are magnetic semiconductors. F errites exhibit ferrimagnetic behaviour and are
widely used as magnetic materials ill various electronic devices. Due to occupancy of
l
cations in two crystallographically different sites (i.e. octahedral B and tetrahedral A
sites) three kinds of magnetic interactions are possible between the metallic IOns,
through the intermediate 0
2
- iOllS, by superexchange mechanism, namely, A-A
interactions, B-B interactions and A - B interactions. These interaction energies are
negative and induce an antiparallel orientation. Calculations show that A-B
interactions are the strongest and hence, for inverse spinels, the resultant magnetic
moment is that of the divalent metal ion in B sites. This can be explained by taking
magnetite (Fe
3
04) as a specific example. It has the inverse spinel cation
[Fe
2
+ Fe
3
] oct 0
4
. The spins of A site and B site Fe
3
+ ions mutually cancel due
to negative A-B interaction and the resultant moment is only due to the ions in the
B sites. But in ZnFe204, a normal there can be neither A-B nor A-A interaction
as Zn
2
+ is a non- magnetic ion. Therefore, the only prevalent interaction is B-B
between Fe
3
+ ions, which is antiferromagnetic [68]. The other normal ferrite CdFe204
also exhibits similar behaviour.
Spinel ferrites in general are semiconductors with conductivity ranging between
10
2
and 10-
11
ohm-
1
cm
1
The low electrical conductivity compared to conventional
metallic magnetic materials is responsible for their wide use at microwave frequencies.
Ni-Zn ferrites have been found to be one of the most versatile ferrites for general use.
This microwave behaviour of Ni-Zn ferrites strongly depends on their composition
[69]. Co-Zn ferrites [70] and lithium ferrites [71] were also extensively studied in
technological fields.
1.2.5 Spinels as Catalysts
Spinels show interesting catalytic properties. In these compounds the properties
are controlled by the nature of the ions, their charge and site distribution among the T-
and 0 - sites. The catalytic activity of spinels containing transition metal ions is
influenced both by the redox properties and the acid-base properties of these ions
.Correlation between catalytic activities and the electric or magnetic properties of
22
spinels is often found; this is a direct consequence of the dependence of both properties
on cation distribution among the T and sites. Beaufils and Barbaux [72] have
shown, from surface neutron differential diffraction (SDD) studies, that the surfaces of
ideal nonnal spine Is consist of a mixture of (Ill) and (110) planes. In the case of a
distorted spine 1 like 'Y alumina,jit is suggested that nearly 80% of the exposed faces
are of the (110) type. Probing the surface of solids has become more accurate after
introducing Low Energy Ion Scattering (LEIS) technique in catalytic field. The most
characteristic feature of this technique is that the peaks in the spectra result from
scattering by topmost atomic layer only. Jacobs et al. [73], in a recent work, applied
this technique to evaluate spinel surface composition. Their work clearly revealed that
octahedral sites are exposed ahnost exclusively at the surface of spinel oxide powders
and the catalytic activity of many such systems is mainly due to octahedral cations.
Similar conclusions have been made earlier with regard to oxidation reactions [74].
The fact that tetrahedral sites are not active could originate form stronger
bonds due to the lower valency and coordination number.
Catalytic activities of spinels have been well-established for reactions like
oxidative dehydrogenation of hydrocarbons, hydrodesulphurisation of petroleum
crudes, treatment of automobile exhaust gases, oxidation of carbon monoxide,
hydrogen and methane etc. Unlike single oxides, binary and ternary oxides
show extra structural stability, greater activity and reusability as catalysts. Among the
spinel compounds, ferrites have been used as effective catalysts for a number of
industrially important reactions as mentioned above. The catalytic effectiveness of
ferrites arises because of the ease with which iron can exchange its oxidation state
between 2 and 3. Another important attribute, from the commercial standpoint, is their
stability under extremely reducing conditions, which is due to the spinel structure.
Thus reduction of Fe
3
+ to Fe
2
+ takes place without altering the lattice configurations
so that upon reoxidation, the original state is retained [75].
Spinel ferrites are well-known as effective catalysts for the oxidative
dehydrogenation (OXD) of hydrocarbons containing 4 to 6 carbon atoms. The first
use of magnesium ferrite for this purpose was reported in a patent granted to Bajars,
Croee and Gabliks [76]. Zine-chromium-ferrite showed high conversion and
23
selectivity for the OXD of butene to butadiene [77]. Massoth and Scapiello [7S]
probed the catalyst function in the above case by measuring catalyst weight loss in a
reducing atmosphere of either hydrogen or butene in a flow type microbalance reactor
and also proposed a mechanism fqr the reaction. They found that the spinel ferrites
were less reducible than Fe203 in'hydrogen and underwent only surface reduction in
butene maintaining the chemical ~ . m d structural stability of the bulk. The same reaction
was also investigated over MgFe2q4 catalyst using deuterium. and 14C labelled isotopic
,
tracers to unravel its kinetics and mechanism [79]. The results showed that the
reaction was zero order in oxygen and first order in butene at low partial pressure of
butene and that a modified MassothScarpiello mechanism was operative.
The spinels ACr204 and AFe204 where A = N ~ Co or Mn have been found to
be active for the non-selective oxidation of propylene to C02 and water, the normal Cr
(llI) spinels being more active than the inverse Fe(ITI) spinels [SO].
Decomposition of alcohols is another class of reactions catalysed by oxidic
spinels. The decomposition of propan-2-01 to acetone was studied over chromite
spinels of Zn, Co and Cu [SI]. The resuhs showed that CuCr204 was the most
effective catalyst and the dehydration activity was only meagre. The same
decomposition was studied over MgAh-xFex04 ( x ~ 0.4 and x ~ 1.3 ) systems [75].
Here the catalysts showed both dehydration and dehydrogenation activities for
x > 0.02. The important conclusion was that, the dehydration as well as the electrical
and magnetic properties are influenced by a fundamental property of the spinel
system, namely, the symmetry of the catalytically active Fe
3
+ site. Dube and Darshane
investigated the spinel systems, Znl-xCuxMnFe04 ( 0 ~ x ~ 1 ) [S2] and
C01+x Fe2-2xTix04[83] by various physico-chemical methods and correlated the physical
properties with their catalytic behaviour in benzyl alcohol decomposition. It was
found that Cu-rich catalysts were always more active than Zn-rich catalysts and that
COFe204 was a better catalyst than CO2 Ti04. Cyclohexanol decomposition was also
studied using ZnxNh-xFe204 (0 x ~ 1) [S4] and Mg).xZnxAh04 ( 0 ~ x ~ 1 ) [S5]
spinel systems and the results were correlated with structural parameters.
24
Perhaps the most widely studied reaction using spinel catalysts is the catalytic
selective oxidation of carbon monoxide. Selective removal of carbon monoxide from
COIH
2
mixed gas is a key step for fuel cell or sensor technology. A possible approach
includes selective catalytic oxidation [86,87]. Among metal oxides, cobalt oxide of
~
the spinel type (C0
3
0
4
) is the rhost active catalyst for oxidation of CO. The active
cobalt species for selective oxidation of CO has been found to be C0
3
+ Oh, after
investigating the catalytic activities of ZnC0204, COA!z04. CoFe204 of the spinel type
[87]. The same conclusion has been confirmed by X-ray photoelectron spectroscopy
(XPS) on cobalt spinel oxides such as Zn
x
C0
3

x
0
4
( x ;:::: 0 - 1 ), Al
x
C0
3
-
x
0
4
( x;:::: 1 - 2.5 ) and FexC03-xO 4 (x;:::: 1 - 2.5 ) [88].
Maltha et af. [89] investigated the active sites in the spinels Mn
3
0
4
and C0
3
0
4
in the selective reduction of nitrobenzene to nitrosobenzene by substitution of Mn or
Co ions in T-sites and/or in O-sites by redox inactive ions like Zn and Al. The totally
substituted spine Is ZnMn
2
0
4
, CoAh04 and ZnC0
2
0
4
showed that the Mn and Co ions
in octahedral positions were responsible for the activity of the reaction. MnAh04
however showed some activity for the reaction which should be due to surface
enrichment and/or oxidative transfer of manganese from T - to 0 - sites. The same
team of researchers studied the cation distribution in the spinels, Znl-xMnxAh04 (0 x
~ 1 ) by X- ray diffraction and MAS-mviR [90] which gave evidence for oxidative
transfer of manganese as Mn
3
+ into O-sites. The compOlmds showed a defect spinel
structure containing MnH and cation vacancies, with average valence of Mn close to
2.8.
Production of methyl formate (MF) is a synthetically important reaction and is
usually achieved by the dehydrocoupling of methanol using copper containing
catalysts. MF was produced in about 50% yield with methanol conversion above 60%
at 320C in patent literature [91,92]. Sato et al. [93] prepared CuO - Ah03 systems
with different Cui AI ratios by the amorphous citrate process and examined their
catalytic activities for the dehydrocoupling of methanol to methyl formate. CuO-
Ah03 samples calcined at temperatures below 1000C are partially reduced during the
catalytic reaction and the selectivity to lvIF decreases with increasing Cu (0) content.
This is because Cu (0) decomposes MF to methanol and CO above 210C. On the
other hand, CuAh04 samples calcined at 1100C showed the highest activity for the
25
fOrmation of MF at a temperature of 310C. The Cu (11) species in CuAh04 were
fOund to be effective sites for the rcaction above 250C.
Spinel catalysts also find ~ e in higher alcohol synthesis. e.g., a commercial
Zn/Cr spinel methanol synthesis c!talyst (Englehard Zn - 0312) has been promoted
with various amounts of K and tested for isobutanol synthesis [94]. An equimolar
mixture of mcthanol and isobutanol is an ideal feedstock for producing the high octane
petrol additive, methyl tertiary butyl ether (MTBE). The use of 3 wt % K- containing
catalysts resulted in the lowest methanol- to- isobutanol mole ratio of 1.5, which is
close to the desired ratio of 1 for MfBE synthesis.
Hctcrogcneous decomposition of H
2
0
2
is a convenient alternative method to
electrolysis of water, for the production and storage of oxygen gas. The usual peroxide
decomposition catalysts like silver oxide, platinum black etc. are expensive. Various
ferrospinels have been reported as effective catalysts for H
2
0
2
decomposition [95-99].
Spine Is of general formula MxFe).x04 where M = Co, Ni or Cu and
o x 3 have been found to be very active for peroxide decomposition in alkaline
media, with the activity following the order, Co>Cu >Ni [96-98]. Sengupta and Lahiri
[99] investigated the intrinsic catalytic activity of several coprecipitated Mn
x
Fe3-
x
04
specimens having x varying between 0.5 to 2.5 , towards hydrogen peroxide
decomposition in neutral media. [Link].s04 has been found to be more active and
COFe204 as much active as the noble metal catalysts for the above reaction in neutral
media [99].
Liquid phase Friedel -Crafts alkylation of benzene with benzyl chloride has
been studied using CuCr2_xFex04 spinel catalysts [100]. CuCr204 gave no reaction but
the yield of the product diphenyImethane increased with iron content in the spine!,
reaching a maximum with CuFe
2
04. Presence of strong Lewis acid sites as proved by
DRIFT spectra of adsorbed pyridine on the spinels was suggested as mainly
responsible for the good catalytic performance.
The catalytic activity of a senes of ferrites of the general formula
Zn!'lI.CoxFe204 ( 0 ~ x 1 ), prepared by 'soft' chemical route has been investigated for
26
aniline alkylation reaction using methanol and dimethyl carbonate (DMC) as the
alkylating agents [101-102]. Methanol showed high N-monoalkylation selectivity
compared to DMC and the most active and stable catalyst has been found to be
[Link].2Fe204. The above catalysts are also found to be very effective, CoFeZ04
being the best, for the alkylatioJ of phenol to o-cresol and 2,6-xylenol [103]. The
kinetic parameters of N-monoalkylation of aniline with methanol over the above
mentioned catalysts have also been determined [104].
In addition to the above mentioned reactions, lot of other reactions are also
catalysed by spinel type oxides. e.g. Ferrospinels, especially of Co, Ni and Cu, have
been widely patented as alternate catalysts to noble metals for purification of
automobile exhausts. Another example is the hydrodesulphurisation of petroleum
crude with COFez04 and NiFel04 [105].
1.3 SURFACE ELECTRON DONOR PROPERTIES
Study of electron-donor (EO) properties of metal oxides by the adsorption of
electron acceptors (EA) of varying electron affinity values has been a well-established
technique.
It was already known that acidic centres of the Lewis type on active aluminas
could promote the formation of positive radical ions from aromatic hydrocarbons in
presence of molecular oxygen [106]. But the first experimental evidence for the
presence of electron-donor sites on metal oxides was obtained by Flockhart et al.
[107] by studying the esr spectrum of tetracyanoethylene (TCNE) on alumina. The
dipolar nature of aluminas has been confirmed by Flockhart et al. [108-109] using the
electron acceptor perylene and the electron-donor, TCNE. When TCNE was adsorbed
on the surface, the corresponding anion radical was formed. The electron-donor sites
were associated with surface hydroxyl groups and with defect centres involving oxide
ions. Similar studies to determine the number of electron-donor sites were done on
many single and two-component metal oxides [110-113].
The above studies were limited to determining the number of electron-donor
sites only. The first systematic study of determining the strength and distribution of
27
electron-donor sites by adsorption of several electron acceptors over a range of
. electron affinity values, was done by Meguro and Esumi [114-115]. They studied
a1umina, titania and zirconia-titania by adsorption of four electron acceptors namely
7,7,8,8 - 2,5 - dichloro-p- benzoquinone (DCQ), p-
j
dinitrobenzene (PDNB) and m-dinitrobenzene (MDNB) whose electron affinity values
varied from 2.84 to 1.26 eV, using esr spectrometer.
The electron donor strength of metal oxides can be defined as the conversion
power of an electron acceptor adsorbed on the surface into its anion radical [115]. If a
strong EA is adsorbed on the metal oxide, its anion radical is formed at every donor
site present on the metal oxide surface. On the other hand, if a weak EA is adsorbed,
the formation of anion radical will be expected only at the strong donor sites. Finally,
in the case of very weak EA adsorption, the anion radical will not be formed even at
the strongest donor sites. Therefore, the electron donor strength of a metal oxide can be
expressed as the limiting electron affinity value at which free anion radical formation
is not observed at the metal oxide surface. It was concluded that the ED strength of
alumina and titania is similar and stronger than that of zirconia-titania.
The metal oxides, after adsorption of EA from acetonitrile solution, developed
characteristic colours due to the charge transfer (CT) spectra of the adsorbed species.
These coloured samples showed unresolved esr bands proving the existence of radical
ions. Radical concentrations were calculated by comparison of the areas obtained by
double integration of the esr signals of the sample and a standard reference. It was
found that the limiting radical concentration was proportional to the limiting amount of
EA adsorbed and these decreased with decrease in the electron affinity values of the
EA. A plot of logarithm of the limiting radical concentration for a given oxide vs.
the electron affinity of the EA was linear. This was interpreted in tenns of the
distribution of strength of the ED sites; the greater the gradient of these plots, the wider
the distribution. Alumina showed a wider distribution compared to titania or zirconia-
titania.
ED sites come from two sources: electrons trapped in intrinsic defects (created
only at high activation temperatures) and the other, surface hydroxyl or oxide ions. The
ionisation potential of hydroxyl ions is comparatively small (about 2.6 eV in gas
28
phase) and, therefore, a process of the type, Off + A ~ OH + A- , where A is the EA,
can be included [114].
Cordischi et al. [116,117] studied the esr hyperfine splitting parameters of
adsorbed nitrobenzene radical aBions on several metal oxides activated below 1200 K.
j
They found evidence for a dual quality for the ED sites, as consisting of a
coordinatively unsaturated oxide ion ( Orus
2
- ) associated with a nearby Off group
(Bronsted acid site) whose proton interacts with the radical formed.
A-...... W
.
(Me n+ = surface cation, A = EA molecule)
Esumi et al. [118] investigated the ED property of zirconia at various calcining
temperatures (300 -lOOOC) by means of adsorption of TCNQ and found that the
radical concentration decreased with increasing calcining temperatures, reached a
minimum at 7000C and then increased. The behaviour was interpreted in terms of two
different ED sites, surface OH' ions at low temperatures and surface oxide ions at high
temperatures. From the ratio of radical concentration to the amount adsorbed, it was
proved that surface oxide ions were much stronger ED sites than surface Off ions.
The same team [119] also studied the adsorption of various EAs on titania and could
determine that the limit of electron transfer from titania surface to the acceptor ranged
between 1.77 to 1.26 eV in the electron affinity of the acceptor.
Adsorption of EAs from non-aqueous solutions onto solid surfaces shows
various solvent effects. Hosaka and Meguro [120] studied the solvent effect of several
aromatic solvents on the eT adsorption of TCNQ onto various kinds of oxides. Two
different types of influence on radical concentrations were noticed - (i) in insulators
(magnesia, alumina and silica) the radical concentration decreased with decreasing
ionisation potential of the aromatic solvent and (ii) in n-type semiconductors (zinc
oxide and titania), no regular relation between ionisation potential of solvents and
radical concentration was observed. The electron-donor-acceptor interactions on
alumina and titania were probed by means of TCNQ adsorption from solvents of
29
varying basicities and also acidities and the Drago correlation [121] of the heats of acid
- base interactions was applied to the results [122,123]. The adsorption oftetrachloro-
p-benzoquinone (chloranil) from basic and acidic solvents was also studied on the
same metal oxides [124]. The basic solvents used were acetonitrile, ethyl acetate and
1,4 -dioxane and the acidic solveots were dichloromethane and chloroform.
,
The amount of EA adsorbed decreased with increase of acid-base interactions
between the basic solvent and EA and also decreased with an increase in acid-base
interaction between the acidic solvent and electron donor sites of the metal oxides.
Esumi et al. [125] measured the zeta potentials of metal oxides such as alumina
and titania by adsorption of TCNQ from organic solvents of varying basicities and
found that the zeta potentials decreased in the order: acetonitrile> ethyl acetate> 1,4 -
dioxane, the order of increased basic strength of the solvents.
The acid-base and electron-donor properties of rare earth oxides such as Pr601l
[126], Ce02 [127], DY203 [128], Y203 [129-130], Sm2 0 3 [131], La203 [132] and
Nd20 3 [133-134]. and their mixed oxides with alumina were investigated as a function
of composition and activation temperature. The extent of electron transfer was
characterised by magnetic measurements. Again, surface properties and catalytic
activities of mixed oxides such as Ce02-Zr02 [135], Y203-Zr02 [136,137], La203-
ZnO [138] and Ah03-Ce02-DY203 [139] were also investigated.
1.4 ALCOHOL DECOMPOSITION REACTION
It has been well-established that the acidic, basic and redox nature of catalysts
are the most important properties in metal oxide catalysis. Various physico-chemical
methods of determining acidity and basicity of solids have been reviewed by Kijenski
and Baiker [6] who also pointed out that every method has one or other limitation. The
most sensitive probe of catalysts performance will continue to be the rate and
selectivity of a chemical test reaction. In this context, alcohol decomposition has been
widely studied because it is a simple method to determine the functionality of an oxide
catalyst.
There are two basic modes of reaction during alcohol decomposition - (a)
dehydration to fonn an olefin and water and (b) dehydrogenation to form an aldehyde
30
(in the case of primary alcohols) or a ketone (in the case of secondary alcohol) and
hydrogen. At higher temperatures, decomposition may involve carbon-carbon bond
cleavage giving products like CO, C02 etc. At near ambient temperatures, ether can be
a major product. The most widely alcohol decomposition reactions are those of
I
isopropanol and of cycIohexanol. '
According to the generally accepted concept, dehydration is an acidic reaction
whereas dehydrogenation activity is due to the combined effect of both acidic and basic
sites on the system. Isopropanol decomposes to give propene by dehydration and
acetone by dehydrogenation. From a mechanistic point of view, Ai et al. [14, 140,141]
assumed that the dehydration of isopropanol is catalysed by an acid site whereas the
dehydrogenation is catalysed by both acidic and basic sites through a concerted
mechanism. Consequently, the dehydration rate is regarded as a measure of the acidity
of the catalyst while the ratio of the dehydrogenation rate to the dehydration rate, as a
measure of the basicity. However, the widely documented correlation found for
alcohol dehydration is not so clear for alcohol dehydrogenation [142]. Often redox
properties of catalysts are responsible for their oxidation activity and may predominate
over their acid-base properties. According to Krylov [143] dehydrogenation is
expected to be catalysed by p-type semiconductors and dehydration by n-type
semiconductors.
The mechanism of alcohol dehydration can be anyone among El, E2 or ElcB
as outlined in the following scheme: [144] (Fig. 1.4.1)
*
1 X +
X-C-C -H Xli, .... C-C ....
El X-C-C' +W
C=c + HX
Fig. 1.4.1. Three possible routes of dehydration reaction.
]n El, C-OH bond rupture occurs with carbonium ion formation, the latter
being capable of positional and geometrical isomerisation, all possible alkenes being
31
formed. In E2, the reaction is concerted, single step, with no intennediate fonned.
Saytzef alkene orientation occurs from 2-01s, i.e. there are more alk-2-enes than alk-l-
enes. In ElcB, C-H bond repture occurs via the most acidic proton. Hofmann
orientation of alkenes occurs, i.e. alk-l-enes predominate and there is a tendency for
~
dehydrogenation to occur. The above categories are not clear cut and quite often
intermediate situations can occur. The nature of alcohol is of importance and the order
of ease of dehydration is tertiary> secondary> primary. Tertiary alcohols tend to react
by the El mechanism due to the higher stability of tertiary carboruum ion.
Gervasini and Auroux [13] made a 'direct' measurement of acidity and
basicity of a large series of metal oxides microcalorimetrically by adsorption of probe
molecules NH3 and C02. The same authors [145] made an 'indirect' measurement of
acidity and basicity of the same series of oxides from the selectivities of isopropanol
decomposition and attempted to correlate these with the 'direct' values. A relationship
was found between the strength of the acid sites microcalorimetrically evaluated and
the activation energy for the dehydration reaction. But there was no correlation
between the strength of acid or basic sites or both of them and dehydrogenation
parameters.
By using temperature-programmed de sorption-mass spectrometry (TPD-MS)
technique with pyridine (py), 2-6 dimethylpyridine (DMPY) and C02, the
decomposition of I-phenylethanol and 2-propanol have been studied over several oxide
catalysts and the results correlated with acid-base properties [142]. It is known that
DMPY is selectively adsorbed on B r ~ s t e d sites, but not on Lewis sites whereas PY is
adsorbed on both Brq)fisted and Lewis sites. As expected, the dehydration activity was
appreciably correlated to Brq)fisted acidity and total acidity. Bezouhanova et al. [146]
recommend dehydration activity of cyclohexanol decomposition as a simple method of
determining B r ~ s t e d acid sites on a catalyst surface.
The results of cyclohexanol decomposition have also been interpreted similar
to the case of isopropanol. Dehydration of cyclohexanol gives cyclohexene while
dehydrogenation gives cyclohexanone. The cyclohexene activity is related to the
32
surface acidity and the ratio of cyclohexanone to cyc10hexene activity to the surface
basicity [ 147] .
Most of the research work seeking to relate dehydration/dehydrogenation
activity with surface acid - base properties has involved mixed rather than single
oxides as the former provides a of varying acidity through composition changes.
Iron oxide possesses inherent dehydrogenation properties but it was reported that in the
.presence of Ah03 these properties are lost and it becomes a dehydration catalyst [148].
Decomposition of isopropanol was carried out on the solid solution system
MgAh-xFe
x
04 by Narasimhan et al. [75]. The system exhibited both dehydration and
dehydrogenation activities. It was predicted that Fe
3
+ sites act as the active sites for the
adsorption of alcohol while the Fe
3
+ site may be reduced to Fe
2
+ during adsorption and
subsequent reaction. However, it regains the Fe
3
+ state by diffusing the electron to an
adjacent Fe
3
+ ion. In a similar way Gal_
x
Fe
x
CuMn04 spinel system has been studied
for the decomposition of 1- octanol by Dube et al. [149]. They observed that increase
ofFe
3
+ ions at the A site increased the oetyl alcohol decomposition rate. According
to them, when Fe
3
+ replaces Ga
3
+ ions, the number of active centres for the adsorption
of alcohol molecule increases due to the hopping of A site ion between +2 'and +3
states.
Cyclohexanol decomposition has been investigated over the catalyst system
Mgl-
x
Zn
x
Ah04 (0::; x::; 1) [150] and also over ZnxNh-xFe204 [151]. Costa et af. [152]
by means of deuterium labelling experiments, have shown that the gas-phase
dehydration of cyc1ohexanol over a solid zirconium phosphate catalyst, involves a
long-lived carbocation intermediate and that the reaction proceeds via the El
mechanistic route.
1.5 FRIEDEL - CRAFTS ACYLATION REACTIONS
Acylations and alkylations using Lewis acid catalysts such as AlCh, FeCh etc.
and acid catalysts such as CF3S03H, FS03H etc. are important in organic
synthesis and the chemical industry. Acylations are involved in the manufacture of
weed killers, dye intermediates etc. while alkylations are involved in manufacturing
such important chemicals as p-xylene, ethylbenzene, cumene etc. However, these
homogeneous catalytic processes have several disadvantages like the use of large
33
amounts of catalysts, unwanted isomerisations, corrosion of the reactors, environmental
pollution by acidic waste water and spent catalysts, difficulty of catalytic recovery and
so on. To eliminate these disadvantages, the use of soid acid catalysts have been
attempted. Considerable body of literature exists concerning alkylation using solid
acid catalysts. But, relatively fe,W reports exist regarding heterogeneous acylation
reactions.
Solid acids such as heteropolyacids [153], activated iron sulphate [154] and iron
oxide [155] have been attempted for but it was found that these catalysts
dissolved into the reaction mixture during reaction and did not act as true
heterogeneous catalysts.
The first report of a truly heterogenious catalyst for acylation was probably due
to Tanabe [47], who demonstrated that sulphated zirconia was an efficient catalyst for
the acylation of chlorobenzene with o-chlorobenzoyl chloride. Hino and Arata [48]
found the solid superacid, sulphated zirconia, to act as a true and active heterogeneous
catalyst for the acetylation and benzoylation of toluene with acetic and benzoic acids
and benzoic anhydride. The isomer distribution of the methylbenzophenones was para
> ortho meta, similar to the case with homogeneous acylations or aIkylations. The
authors suggested that the adsorption site of the catalyst could be a strong Lewis acid
site at Zr
4
+ created by the inductive effect of S = 0 or a Br?nsted site formed by the
adsorption of water on Zr4+. The same team of researchers [49] reported that alumina
sulphated by 2.5 M H2S04 followed by calcination functioned as a true and very
active heterogeneous catalyst for benzoylation of toluene with benzoyl chloride or
benzoic anhydride. The same reaction was found to be catalysed by several superacidic
sulphated oxides and metal oxide-supported W03 [156]. In most cases, the reaction
showed a continual increase of yield with time, proving them to be heterogeneously
catalytic. In the cases of SOJFe203 and W0
3
/ Fe203, however, the reaction failed to
proceed further after 30-60 minutes, with benzoyl chloride as the acylating agent. In
the latter two cases, the deep brown colour of the reaction mixture was indicative of the
dissolution of FC203 as FeCh. which caused homogeneous catalysis. The catalytic
performance of AI-promoted sulphated zirconia and sulphated titania for benzoylation
of toluene with benzoyl chloride has been investigated [157]. A superacidic
34
perfluororesin sulphonic acid (Nafion-H) has been reported to be catalytically active
for several types of acylation reactions [158].
Benzoylation of toluene [159] and selective benzoylation of o-xylene to 3,4-

dimethylbenzophenone [160] have been reported over zeolite catalysts.
Acylation of aromatics was studied using rare earth (Sc,La,Nd) ion-exchanged
KlO montmorillonite clay as the catalyst [161]. The reaction rate was found to
increase with substrates containing electron-donating groups. Thus benzoylation of
anisole took place giving high yield of products while benzene failed to react.
Electron-donating groups stabilise the benzoyl cation intermediate, PhCO+
Laszlo and Mathy [162] found that transitional metal-exchanged KI0
montmorillonite clay was quite effective for Friedel - Crafts alkylation of
Zr4+ and Ti
4
+, in general, giving the best results.
The liquid phase Friedel-Crafts benzylation of benzene has been investigated
using CuCr2-xFex04 spinel catalysts [163]. DRIFT spectra of adsorbed pyridine
showed the presence of both Lewis and Br;nsted acidic sites on the surface of the
spinels. The number of Lewis acid sites increased as the iron content of the system
increased. Conductivity measurements showed that all the catalysts are
semiconductors, with the activation energy (band gap) decreasing with the iron content.
CuFe204 gave the highest yield of products. The Lewis acidity of the catalysts, coupled
with the low value of activation energy has been suggested as mainly responsible for
the good catalytic performance. Due to the generally unreliable kinetic behaviour of
Friedel-Crafts systems, very few kinetic rate studies of alkylations and acylations were
ever undertaken for the homogeneous systems [164], let alone for the heterogeneous
ones.
It is presumed that the heterogeneous Friedel-Crafts reaction proceeds through
the carbocation or the acyl cation as the intermediate. In the case of superacidic
catalysts, the Br;rtsted acid site can be the active site to produce these intermediate
cations. In other situations, strong Lewis sites are responsible for producing these
cationic intermediates.
1.6 OBJECTIVES OF THE PRESENT WORK
By and large, ferrites are commonly produced by conventional ceramIC
processes involving high temperature solid state reactions between the
constituent oxides/carbonates. These methods have some inherent drawbacks such as
poor compositional control, chemical inhomogeinity, coarser particle size etc. Wet
chemical methods such as hot (100C) coprecipitation, sol-gel method etc. have
overcome these drawbacks and produced fine and homogeneous ferrite powders.
Recently there are reports of preparing spinel ferrites by the low temperature
controlled chemical coprecipitation method using aqueous solutions of the metallic
nitrates and sodium hydroxide as the precipitating agent [165]. So, in this work we
prepared some ferrospinels containing Co, Ni and Cu, by adopting this soft chemical
route. Two series of ferrospinels of fonnula Ni1-xCuxFe204 and Co1-xCuxFf204 where
x varies as O. 0.3, 0.5, 0.7 and 1 were prepared. All these systems have the inverse
spinel structure and only the Co-Cu or Ni-Cu ratio varies in the octahedral sites as x
varies. The acido - basic and redox properties ofthe systems also vary with x.
The discussion of results has been done after sub-dividing the catalytic systems
into simple ferrospinels, AFe104 (A = Co, Ni and Cu) and mixed ferrospinels of the
Ni-Cu series and the Co-Cu series (x = 0.3, 0.5 and 0.7). Following the discovery of
superacidity in sulphated metal oxides, especially zr02, much work has been done on
modifying metal oxides with anions like sulphate, phospshate etc. Since sulphated
Fe20J is one among the solid superacids reported, we have taken up in this work, the
modification of the ferrospinel systems with sulphate ion and investigating their
properties. The main objectives of the present work are the following:
> To prepare ferrospinels of Co, Ni and Cu by low temperature co-precipitation
methods and also their sulphated analogues and characterise these by various
physico-chemical methods like XRD, EDX, BET surface area, FTIR, Mossbauer,
TGAetc.
> To study the effect of copper substitution in the spinel matrix of nickel and cobalt
ferrospinels.
36
) To evaluate the surface basicity using electron acceptors of various electron affinity
values.
) To study the vapour -phase cyc\ohexanol decomposition reaction and correlate the
results with surface acid-base and redox properties.
) To evaluate the surface acidity by gravimetric adsorption ofn-butylamine followed
by TGA and also by the dehydration selectivity of cyclohexanol decomposition.
) To assess the catalytic activity by studying the Friedel-Crafts benzoylation reaction
of toluene.
) Sulphation of oxides is known to create new active sites. .so another objective is
to prepare sulphate-modified analogues of all samples under study and explore
their surface properties and catalytic activities.
) To explore the effect of activation temperature on the properties of the catalysts by
doing the above studies at activation temperatures of 300
0
C and 500
0
C.
) To reaffinn the trends in benzoylation of toluene by doing the benzoylation of
benzene with the ferrospinel samples.
REFERENCES
1. R. H. Perry and D. W. Green, "Perry's Chemical Engineers' Handbook", Seventh
Edition, 1977, p.23

2. F. Greek, Chemical a!ld Engirieering News, 67(22) (1989) 29
3. 1. A. Schwarz, C. Contescu and A. Contescu, [Link]., 95 (1995) 477.
4. M. A. Barteau, [Link]., 96 (1996) 1413
5. K. Tanabe, M. Misono, Y. Ono and H. Hattori, "New Solid Acids and Bases",
Kodansha, Tokyo, 1989, p.l
6. 1. Kijenski and A. Baiker, Catal. Today, 5 (1989) 1
7. H. Pines, 1. A. Vaseley and V. N. Ipatieff, 1. Am. Chem. Soc., 77 (1961) 6314
8. H. Hattori, Chem. Rev., 95 (1995) 537
9. 1. L. G. Fierro and 1. F. Garcia De La Banda, Catal. Sci. Eng., 28 (2&3)
(1986) 265
10. A. Clark, "The Theory of Adsorption and Catalysis", Academic Press, New York
and London, 1970, ch.8
11. R. L. Augustine, ''Heterogeneous Catalysis for the Synthetic Chemist", Marcel

Dekker, Inc., 1996, p.180
12. T. W. Swaddle, "Inorganic Chemistry", Academic Press, 1997, p.122
13. A. Auroux and A. Gervasini, 1. Phys. Chem., 94 (1990) 6371
14. M. Ai and S. Susuki, 1. Catal., 30 (1973) 362
15. Vu. Belokopytov, K. M. Kholyavalenko, M. Ya. Rubanic, Kin. i Kataliz (russ.),
14 (1973) 1280.
16. Vu. Belokopytov, K. M. Kholyavalenko, [Link]. Rubanic, Kataliz i Katalizatory,
Vol.8 (Russ), Naukovaya Dumka, Kiev (1971) 13
17. P. Forzati, F. Trifiro and P. L. Villa, 1. Catal., 52 (1978) 389
37
18. B. Grzybowska - Swierkosz, "Catalysis by Acids and Bases", (Editors: [Link] et
al.), Elsevier, 1985, p. 45
19. (a) K. Tanabe, M. Misono, Y. Ono and H. Hattori, 'New Solid Acids and Bases",
Kodansha, Tokyo, 1989, (b) A. Koyo, T. Yamaguchi, K. Tanabe, 1. Catal., 83
(1983) 99
38
20. K. Arata, K. Sato and 1. Toyoshima, J. Catal., 42 (1976) 221
21. K. Arata, K. Yabe and I. Toyoshima, lCatal.,44 (1976) 385
22. K. Arata and I. Toyoshima, 47 (1977) 109
.. I ..
23. K. Arata, A FulcUl and L Toyoshima, 1. Chem. Soc., Chem. Comrnun., (1978) 121
24. K. Arata and M. Hino, Bull. Chem. Soc. Jpn., 53 (1980) 535
25. K. Kimura, H. Ai, A Ozaki, ICatal.,18 (1970) 271
26. H. Uchida, H. Imai, Bull. Chem. Soc. Jpn., 35 (1962) 995
27. K. Mayura and A Ozaki, BulL Chem. Soc. Jpn., 46 (1973) 351
28. Y. M. Lin, I. Wang and C. T. Yeh, [Link].,41 (1988) 53
29. Ch. Sivaraj, B. M. Reddy and P. K. Rao, Appl. CataI., 45 (1988) IlL
30. Mitsubishi Chem. Ind. Ltd., Jpn, Patent 136241 (1980)
31. K. Tanabe, M. Itoh, K. Morishige and H. Rattori, in "Preparation of Catalysts",
(B. Delmon, P. A Jacob, G. Poncelet, eds.), Elsevier, Amsterdam, 1976, p.65
32. K. Arata, Adv. Catal., 37 (1990) 165
33. K. Tanabe and W. F. Holderich, Appl. CataI., 181 (1999) 399
34. D. Farcasiu and J Qi AppI. Catal., 128 (1995) 97
35. K. Arata and M. Hino, Mater. Chem. Phys., 26 (1990) 213
36. E. Iglesia, S. L. Solid and G. M. Kramer, lCatal., 144 (1993) 238
37. T. Jin, T. Yamaguchi and K. Tanabe, 1. Phys. Chem., 90 (l986) 4794
38. M. Bensitel, O. Saur, J. C. Lavalley and B. A Morrow, Mater. Chem. Phys., 19
(1988) 147
39. V. S. Komarovand M. F. Sinilo, Kinet. Catal. (Engl. Edit.), 29 (1988) 701
40. P. Nascimento, C. Akrotopoulou, M. Oszagyan, G. Coudurier, C. Travers,1. F. Ioly
and 1. C. Vedrine, 10
th
Int. Congr. Catalysis ( Budapest, July 1992) Contr. 080
41. 1. H. Lunsford, H. Sang, S. M. Campbell, C. H. Liang and R. G. Anthony, Catal.
Lett., 27 (1994) 305
42. X. Song and A Sayari, Catal. Rev. - Sci. Eng., 38(3) (1996) 329
43. O. Saur, M. Bensitel, A B. M. Saad,1. C. Lavalley, C. P. Tripp and B. A Morrow, J.
Catal., 99 (1986) 104
39
44. B. A. Morrow, R. A. Mc Farlance, M. Lion and J. C. Lavalley, J. Catal., 107 (1987)
232
45. A Clearfield, G. P. D. A H. Khazi - Catal. Today, 20 (1994) 295
46. F. Babou, B. Bigot and P. 1. Phys. Chem., 97 (1993) 11501
41. K. Tanabe, Meter. Chem. Phys., 13 (1985) 347
48. M. Hino and K. Arata, 1. Chem. Soc., Chem. Commun., (1985) 112
49. K. Arata and M. Hino, Appl. Catal., 59 (1990) 197
50. Y. Xia, W. Hua and Zi Gao, Catal. Lett., 55 (1998) 101
51. K. R. Venkatesh, 1. Hu, J. W. Tiemey and I. Wender, Prepr. Am. Chem. Soc. Div.
Fuel Chem., 40 (1995) 788
52. S. Sugunan, C. R. K. Seena and T. M. Jyothi, React. Kinet. Catal. Lett., 67, 1 (1999)
49
53. S. Sugunan and C. R. Kumaree Seena, Indian 1. Chem., 37A (1998) 438
54. S. Sugunan and C. R. Kumaree Seena, Indian J. Chem., 37A (1998) 669
55. A. R. West, " Solid State Chemistry and its Applications", John Wiley, New York,
1989, p.569
56. D. K. Chakrabarthy, "Solid State Chemistry", New Age International, New Delhi,
1996, p.53
57. B. Viswanathan, "Ferrite Materials - Science and Technology", (B. Viswanathan
and V. R K. Murthy eds. ), Narosha, New Delhi, 1990, p.4
58. G. Blasse, Philips Research Reports Supplements, 3 (1964) 2
59. T. F. W. Barth and E. Posenjak, Zs. Kristallographie, 84 (1952) 325
60. A. F. Wells, "Structural Inorganic Chemistry", 4th Edition, ELBS, London, 1979,
p.491
61. [Link], "Ferrite materials - Science and Technology", (B. Viswanathan and
V. R K. Murthy, eds.), Narosha, New Delhi, 1990, p.5
62. E. 1. W. Verwey, F. de Boer and 1. H van Santen, J. Chem. Phys., 16 (1948) 1091
63. G. Blasse, PhiIips Research Supplements, 3, (1964) 7
64.1. D. Dunitz and L. E. Orgel, Phys. Chem. Solids, 3 (1957) 318
65. D. S. Mc Clare, Phys. Chem. Solids, 3 (1957) 311
.66. A. R. West, "Solid State Chemistry and its Applications", John Wiley, New York,
1989, p.313
67. O. Blasse, Philips Research Repprts, Suppliment, 3 (1964) 13
~
68. [Link], ''Ferrite materials - Science and Technology", (B. Viswanathan
and V. R- K. Murthy, eds.), Narosha, New Delhi, 1990, p.9
69. V. R K. Murthy, Ph.D Thesis, Department of Physics, Indian Institute of
Technology, Madras, India (1981)
40
70. O. S. Josyulu, Ph.D Thesis, Department of Physics, Indian Institute of Technology,
Madras, India (1981)
71. R. Raman, Ph.D Thesis, Indian Institute of Technology, Madras, India (1989)
72.1. P. Beaufils and Y. Barbaux, 1. App1. Crystallogr., 15 (1982) 301
73.1. P. Jacobs, A. Maltha, 1. G. H. Reintjes, 1. Drimal, V. Ponec and H. H. Brongersma,
1. Catal., 147 (1994) 294
74.1. Ziolkowski and Y. Barbaux, 1. Mol. Catal., 67 (1991) 199
75. C. S. Narasimhan and C. S. Swamy, Appl. Catal., 2 (1982) 315
76. L. Bajars, J. L. Croce and M. Gabliks, U. S. Patent 3,284,536 (1966)
77. R. 1. Rennard Ir and W. L. Kehl,l. Catal., 21 (1971) 282
78. F. E. Massoth and D. A. Scarpiello,1. Catal., 21 (1971) 294
79. M. A. Gibson and J. W. Hightower, 1. Cata1., 41 (1976) 420
80. L. Zanderighi, M. P. Faedda and S. Carra, 1. Catal., 35 (1974) 127
81. V. Krishnasamy and S. Chokkalingam, 1. Indian. Chem. Soc., 59 (1982) 641
82. G. R- Dube and V. S. Darshane, 1. Chem. Soc. Faraday Trans., 88(9) (1992) 1299
83. G. R. Dube and V. S. Darshane, Bull. Chem. Soc. Jpn., 64 (1991) 2449
84. N. 1. labarathinam and V. Krishnasamy, in: ''Catalysis: Present and Future",
Intermediate Series on Chemical Engineering, (p. Kanta Rao and R. S. Beniwal,
eds), Publications and Information Directorate and Wiley Eastern Ltd., New Delhi,
1995, p.288
85. M. V. Joshi, S. G. Oak and V. S. Darshane, in: "Catalysis: Modem Trends", (N. M.
Gupta and D. K. Chakrabarthy eds.), Narosha, New Delhi, 1995, p. 275
86. S. H. Oh and R. M. Sinkevitch, 1. Cata1., 142 (1993) 254
41
87. T. Takada, S. Kasahara, K. Omata and M. Yamada, Nippon Kagaku Kaishi, (1994)
793
88. K. Omata, T. Takada, S. KasahR{a and M. Yamada, Appl. Catal . 146 (1996) 255
89. A MaItha, H. F. Kist, B. Brunet! 1. Ziolkowski. H. Onishi, Y. Iwasawa and V.
Ponec,1. Catal., 149 (1994) 356
90. 1. Ziolkowski, A. M. Maltha, H. Kist, E. 1. Grootendorst, H.1. M. de Groot and V.
Ponec, 1. Catal., 160 (1996) 148
91. Mitsubishi Gas Chemical Co., Japan Patent 46,821 (1978)
92. Mitsubishi Gas Chemical Co., Japan Patent 33,418 (1984)
93. S. Sato, M. Iijima, T. Nakayama, T. Sodesawa and F. Nozaki, 1. Catal., 169 (1997)
447
94. W. S. Epling, G. B. Hoflund, W. M. Hart and D. M. Minahan, 1. Catal., 169 (1997)
438
95. H. M. Cota, J. Katan, M. Chin and F. J. Schoenweis, Nature, London, 203 (1964)
1281
96.1. R Goldstein and A. C. C. Tseung. J. Catal., 32 (1974) 452
97. A 1. Onuchukwu, 1. Chem. Soc. Faraday Trans., 180 (1984) 1447
98. A I. Onuchukwu and A. B. Zuru, Mater. Chem. Phys., 15 (1986) l31
99. S. K. Sengupta and P. Lahiri, Indian J. of Technol., 30 (1992) 1 7 2 ~
P. Lahiri and S. K. Sengupta, Can. 1. Chem., 69 (1991) 33
100. S. P. Ghorpade, V. S. Darshane and S. G. Dixit, Appl. Catal., 166 (1988) l35
101. K. Sreekumar, T. M. Jyothi, M. B. Talwar, B. P. Kiran, B. S. Rao and S.
Sugunan, J. Mol. Catal., 152 (2000) 225
102. K. Sreekumar, T. Mathew, S. P. Mirajkar, S. Sugunan and B. S. Rao, Appl.
CataJ., 201 (2000) Ll
103. B. S. Rao, K. Sreekumar T. M. Jyothi, Indian Patent No. 2707/98, (1998)
104. K. Sreekumar, T. M. Jyothi, C. G. Ramankutty, B. S. Rao and S. Sugunan, React.
Kinet. Catal. Lett., 70,1 (2000) 161
105. P. N. Rylader. Jr and W. 1. Zimmerschied, U. S. Pat. 2,805 (1957) 187
106. R K. Merrifield and W. D. Plillips, 1. Am. Chem. Soc. 80 (1958) 2778
42
107. B. D. Flockhart, C. Naccache, J. A. N. Scott and R. C. Pink, Chemical
Communications, 11 (1965)
108. B. D. Flockhart, J. A. N. Scott and R. C. Pink, Trans. Faraday Soc., 62 (1966)
370
109. B. D. Flockhart, I. R. Leith and R. C. Pink, Trans. Faraday Soc., 65 (1969) 542
110. A.J. Tench and R. L. Nelson, Trans. Faraday Soc., 63 (1967) 2254
Ill. M. Che, C. Naccache and B. Imelik, J. Catal., 24 (1972) 328
112. H. Hosaka, T. Fujiwara and K. Meguro, Bull. Chem. Soc. Jpn., 44 (1971) 2616
113. H. Hosaka, N. Kawashima and K. Meguro, Bull. Chem. Soc. Jpn., 45 (1972)
3371
114. K. Meguro and K. Esumi, J. Colloid Interface Sci., 59,(1) (1977) 93
115. K. Esumi and K. Meguro, J. Colloid Interface Sci., 66 (1978) 192
116. D. Cordischi and V. Indovina, J. Chem. Soc. Faraday Trans., 72(10) (1976) 2341
117. D. Cordischi, V. Indovina and A. Cinimo, J. Chem. Soc. Faraday 1, 70 (1974)
2189
118. K. Esumi and K. Meguro, Bull. Chem. Soc. Jpn., 55 (1982) 315
119. K. Esumi andK. Meguro, Bull. Chem. Soc. Jpn., 55 (1982) 1647
120. H. Hosaka and K. Meguro, Colloids and Polymer Sei., 252 (1974) 322
121. R S. Drago, L B. Parr and C. S. Chamberlain, J. Am. Chem. Soc., 99 (1977)
3203
122. K. Esumi, K. Miyata andK. Meguro, Bull. Chem. Soc. Jpn., 58 (1985) 3524
123. K. Esumi, K. Miyata and F. Waki and K. Meguro, Colloids and Surfaces, 20
(1986) 81
124. K. Esumi, K. Miyata, F. Waki and K. Meguro, Bull. Chem. Soc. Jpn., 59 (1986)
3363
125. K. Esumi, K. Magara and K. Meguro, J. Colloid Interface Sci., 141, (2) (1991)
578
126. S. Sugunan, G. D. Devikarani and P. A. Unnikrishnan, J. Mater. Sci. Technol., 10
(1994) 425
127. S. Sugunan and J. M. Jalaja, Collect. Czech. Chem. Commun., 59 (1994) 2605
128. S. Sugunan K. B. Sherley and G. D. Devikarani, React. Kinet. CataI. Lett.,
51(2) (1993) 525
129. S. Sugunan and G. D. Devi4rani, 1. Mater. Sci. Lett., 10 (1991) 887
130. S. S u g u n ~ G. D. DevikaraAi and P. A. Unnikrishnan, Indian J. Eng. Mater.
Sci., 12 (1995) 245
131. S. Sugunan and 1. J. Malayan, J. Adhesion Sci. TechnoL, 9(1) (1995) 73
132. S. Sugunan and K. B. Sherley, Indian 1. Chem., 32(A) (1993) 689
133. S. Sugunan and G. D. Devikarani, Indian 1. Chem., 32(A) (1993) 993
134. S. Sugunan and G. D. Devikarani J. Mater. Sci., 29 (1993) 4811
135. S. Sugunan and B. Varghese, Indian J. Chem., 37A (1998) 806
136. S. Sugunan and Anto Paul, React. Kinet. Catal. Lett., 65 (2) (1998) 343
137. S. Sugunan and Anto Paul, Indian J. Chem., 36A (1997) 1068
138. S. Sugunan and Binsy Varghese, React. Kinet. Catal. Lett., 62 (I) (1997) 157
139. S. Sugunan and Bindu Jacob, Indian 1. Eng. Mater. Sci.,4 (1997) 120
140. M. Ai,1. Catal., 40 (1975) 318
141. M. Ai, Bull. Chem. Soc. Jpn., 50 (1977) 2597
142. M. A. Aramendia, V. Borau, I. M. Garcia, C. Jimenez, A. Marinas, 1. M.
Marinas, A. Porras and F. 1. Urbano, Appl. Catal., 184 (1999) 115
143. O. V. Krylov, "Catalysis by Non-metals ", Academic Press, New York.
43
144. H. Vinek, H. Noller, M. Ebel and K. Schwarz, 1. Chem. Soc., Faraday Trans.I, 73
(1977) 734
145. A Auroux and A. Gervasini, 1. Catal., 131 (1991) 190
146. C. P. Bezouhanova and M. A. Al-Zihari, Catal. Lett., 11 (1991) 245
147. D. Martin and D. Duprez, 1. Mol. Catal., 118 (1997) 113
148. R Venkatachalam and 1. C. Kuriakose, Proc. Natl. Acad. Sci., India, Sect. Al
(1977) 245
149. G. R Dube and V. S. Darshane, 1. Mol. CataI., 79 (I 993) 285
ISO. M. V. Joshi, S. G. Oak and V. S. Darshane, in "Catalysis: Modem Trends" (N.
M. Gupta and D. K. Chakrabarthy ,eds. ), Narosha Publishing House, New
Delhi, 1995, p. 275
151. N. 1. Iabarathinam and V. Krishnasamy in, "Catalysis - Present and Future",
edited by P. Kanta Rao and B. S. Benwal, Publication And Information
Directorate & Wiley Eastern Ltd., New Delhi, 1995, p. 288
'l'
44
152. M. C. C. Costa, L. F. Hudson. R. A W. Johnstone, 1. Y. Liu and D. Whittaker, J.
Mol. Catal., 142 (1999) 349
153. K. Nomiya, Y. Sugana, S. Sosa and M. Miwa, Bull. Chem. Soc. Jpn, 53 (1980)
2089
154. K. Arata and M. Hino, Bull. Chem. Soc. Jpn, 53 (1980) 446
155. K. Arata and M. Hino, Chem. Lett., (1980) 1479
156. K. Arata H. Nakamura and M. Shouji, Appl. CataI., 197 (2000) 213
157. Y. Xia, W. Hua and Z. Gao, Catal. Lett., 55 (1998) 101
158. G. A Olah, P. S. Iyer and G. K. Surya Prakash, Synthesis, (1986) 513
159. A P. Singh, D. Bhattacharya and S. Sharma, 1. Mol. Catal., 102 (1995) 139
160. B. Jacob, S. Sugunan and A P. Singh, 1. Mol. Catal., 139 (1999) 43
161. D. B. Barbier, A Dormond and F. D. Montagne, 1. Mol. Catal., 149 (1999) 215.
162. P. Zaszlo and A Mathy, Helvetica Chimica Acta, 70 (1987) 577
163. S. P. Ghorpade, V. S. Darshane and S. G. Dixit, Appl. Catal., 166 (1998) 135
164. G. A 01a11, S. Kobayashi and M. Tashiro, 1. Am. Chem. Soc., 94 (1972) 7448
165. P. S. Anilkumar, 1. 1. Shrotri S. D. Kulkarni, C. E. Deshpande and S. K. Date,
Mater. Lett., 27 (1996) 293