Name:Sapnil Vernekar

Roll No;SU190299
Class:TY.BSc.
Course title:E.15 ,Selected Topics in Inorganic
chemistry.
Date of Submission:20-05-2022

1.WRITE A NOTE ON FULLERENES AND

FULLERIDES.
FULLERENES
A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by
single and double bonds so as to form a closed or partially closed mesh, with fused rings of five
to seven atoms. The molecule may be a hollow sphere, ellipsoid, tube, or many other shapes and
sizes. 

Structure of Fullerene
Fullerenes in their natural form tend to be highly symmetrical. Their structure is quite similar to
that of graphite and is made up of a sheet of connected hexagonal rings (cage structure).
However, they have pentagonal and sometimes heptagonal rings which do not allow the sheet to
become planar. They are often referred to as buckyballs and buckytubes depending on their
shape. Cylindrical fullerenes are referred to as nanotubes. 
 The C60 fullerene (buckminsterfullerene).
In any case, there is an infinite number of fullerenes that can exist. Fullerenes can be C60, C70,
C80, and C90 existing in various forms. This depends largely on the number of carbon atoms
present in the molecule. Nonetheless, their structure is primarily based on pentagonal and
hexagonal rings that are constructed as per the rules for making icosahedra.

Properties of Fullerene
the physical and chemical properties of fullerene.

Physical Properties of Fullerene

 Its behaviour and structure depend on the temperature. As the temperature is increased
fullerene gets converted into the C70. 
 Fullerene structure can change under different pressures.
 Fullerene has an ionization enthalpy of 7.61 electron volts.
 Its electron affinity is 2.6 to 2.8 electrons volts.

Chemical Properties of Fullerene

 Fullerenes are stable, but not totally unreactive.

 In chemical reactions, fullerene can act as an electrophile.
 It acts as an electron-accepting group and is characterized as an oxidizing agent.
 Fullerenes when doped or crystallized with alkali or alkaline earth metals it showcases
superconductivity properties.
 Fullerene is ferromagnetic.
 Some fullerenes are inherently chiral.
 It is soluble in organic solvents such as toluene, chlorobenzene, and 1,2,3-
trichloropropane.
Types of Fullerene
Fullerenes exist in two major families depending on some distinct properties and applications.
The two families include the closed buckyballs and the open-ended cylindrical carbon nanotubes.
However, there are also hybrid structures that can exist between these two classes. They can be
carbon nanobuds which are basically nanotubes capped by hemispherical meshes or larger
“buckybuds”.
Buckyball Clusters
These fullerenes are basically unsaturated versions of dodecahedra. These are also some of the
smallest members of the fullerene group. Its structural formula is C20.
Buckminsterfullerene
Buckminster-fullerene is the smallest fullerene molecule. It contains pentagonal and hexagonal
rings and no two pentagons will share an edge. 
Buckminster-fullerene exists in C60 form is the most common in terms of natural occurrence. The
structure of buckminsterfullerene is a truncated icosahedron similar to that of a football.
Linked Ball and Chain Dimer: In this type of fullerene, two buckyballs are mainly linked by a
carbon chain. There are also other fullerenes such as heterofullerenes which have heteroatoms
substituting carbons in a cage or tube-shaped structures. Then there is metallofullerene whose
molecule is composed of a metal atom trapped inside a fullerene cage.
Carbon Nanotubes
This type of fullerene has cylindrical or hollow tubes of very small dimensions; they are mostly a
few nanometers wide. However, they can also be micrometre to several millimetres in length.
Talking about some of the properties of carbon nanotubes, they can be both closed and open-
ended. As a result of their unique molecular structure, they have some unique macroscopic
properties. Some of them include including high tensile strength and electrical conductivity, high
ductility and heat conductivity including relative chemical inactivity. Another form that we find
is the megatubes. These are slightly bigger in diameter than nanotubes and are generally found
with walls of different thicknesses. 

Production of Fullerene
Fullerene preparation starts with the production of fullerene-rich soot. The method that was used
to produce fullerene involved sending a large electric current between two nearby graphite
electrodes in an inert atmosphere. The electric arc that was created vaporized the carbon into a
plasma that then cooled into the sooty residue. Alternatively, the soot can also be produced by
laser ablation of graphite or pyrolysis of aromatic hydrocarbons. Combustion is the most
efficient process that was used.
These methods usually resulted in the production of different fullerenes in various mixtures and
other forms of carbon. So the fullerenes are then basically extracted from the soot using
appropriate organic solvents. Usually, the mixture is separated by chromatography.
Uses of Fullerenes

 Fullerenes are used in the medical field as light-activated antimicrobial agents.

 It is also used in several biomedical applications including the design of high-
performance MRI contrast agents, X-ray imaging contrast agents, photodynamic therapy
and drug and gene delivery.
 Buckminsterfullerene is used in drug delivery systems, in lubricants and as a catalyst.
 It is also used as a conductor.
 Some types of fullerene can be used as an absorbent for gases.
 It is used in making cosmetic products.
 C60  based films are used for photovoltaic applications.
 Fullerenes are used in making carbon nanotubes based fabrics and fibres.

Fullerides
Fullerides are chemical compounds containing fullerene anions. Common fullerides are
derivatives of the most common fullerenes, i.e. C60 and C70. The scope of the area is large
because multiple charges are possible, i.e., [C60]n− (n = 1, 2...6), and all fullerenes can be
converted to fullerides. The suffix "-ide" implies their negatively charged nature.
Fullerides can be isolated as derivatives with a wide range of cations. Most heavily studied
derivatives are those with alkali metals, but fullerides have been prepared with organic cations.
Fullerides are typically dark colored solids that generally dissolve in polar organic solvents.
According to electronic structure calculations, the LUMO of C60 is a triply degenerate orbital of
t1u symmetry. Using the technique cyclic voltammetry, C60 can be shown to undergo six
reversible reductions starting at −1 V referenced to the Fc+/Fc couple. Reduction causes only
subtle changes in the structure and many derivatives exhibit disorder, which obscures these
effects. Many fullerides are subject to Jahn–Teller distortion. In certain cases, e.g. [PPN]2C60,

Preparations
are highly ordered and slight (10 pm) elongation of some C−C bonds is observed.treating with
alkali metals to give the alkali metal fullerides:
C60 + 2 K → K2C60
 treating with suitable organic and organometallic reducing agents, such
as cobaltocene and tetrakisdimethylaminoethylene.
 alkali metal fullerides can be subjected to cation metathesis. In this way the
(bis(triphenylphosphine)iminium (PPN+) salts have been prepared, e.g. [PPN]2C60:[1]

K2C60 + 2 [PPN]Cl → [PPN]2C60 + 2 KCl

The fulleride salt ([K(crypt-222)]+)2[C60]2− salt is synthesized by treating C60 with
metallic potassium in the presence of [2.2.2]cryptand.

Alkali Metals and It’s Derivatives

attention has been paid to alkali metal (Na+, K+, Rb+, Cs+) derivatives of C603− because these
compounds exhibit physical properties resulting from intercluster interactions such as
metallic behavior. In contrast, in C60, the individual molecules interact only weakly, i.e.
with essentially nonoverlapping bands. These alkali metal derivatives are sometimes
viewed as arising by intercalation of the metal into C60 lattice. Alternatively, these
materials are viewed as n-doped fullerenes.[2]
Alkali metal salts of this trianion are superconducting. In M3C60 (M = Na, K, Rb), the M+ ions
occupy the interstitial holes in a lattice composed of ccp lattice composed of nearly
spherical C60 anions. In Cs3C60, the cages are arranged in a bcc lattice.
In 1991, it was revealed that potassium-doped C60 becomes superconducting at 18 K
(−255 °C).[3] This was the highest transition temperature for a molecular superconductor.
Since then, superconductivity has been reported in fullerene doped with various other
alkali metals.[4][5] It has been shown that the superconducting transition temperature in
alkaline-metal-doped fullerene increases with the unit-cell volume V. [6][7] As Cs+ is the
largest alkali ion, caesium-doped fullerene is an important material in this family.
Superconductivity at 38 K (−235 °C) has been reported in bulk Cs3C60,[8] but only under
applied pressure. The highest superconducting transition temperature of 33 K (−240 °C)
at ambient pressure is reported for Cs2RbC60.[9]
The increase of transition temperature with the unit-cell volume had been believed to
be evidence for the BCS mechanism of C60 solid superconductivity, because inter
C60 separation can be related to an increase in the density of states on the Fermi
level, N(εF). Therefore, efforts have been made to increase the interfullerene separation,
in particular, intercalating neutral molecules into the A3C60 lattice to increase the
interfullerene spacing while the valence of C60 is kept unchanged. However, this
ammoniation technique has revealed a new aspect of fullerene intercalation
compounds: the Mott transition and the correlation between the orientation/orbital order
of C60 molecules and the magnetic structure.[10]
Fourfold-reduced materials, i.e., those with the stoichiometry A 4C60, are insulating, even
though the t1u band is only partially filled.[11] This apparent anomaly may be explained by
the Jahn–Teller effect, where spontaneous deformations of high-symmetry molecules
induce the splitting of degenerate levels to gain the electronic energy. The Jahn–Teller
type electron-phonon interaction is strong enough in C 60 solids to destroy the band
picture for particular valence states.[10]
A narrow band or strongly correlated electronic system and degenerated ground states
are relevant to explaining

2.With Respect to Zeolites, Explain the structure,

Synthesis and applications.
Zeolites are microporous, three-dimensional crystalline solids of aluminium silicate. Zeolites
have small openings of fixed size in them which allow small molecules to pass through them
easily but larger molecules cannot pass through them; that is why they are sometimes called
molecular sieves.

Structures.

The crystalline structure of zeolite is very different as compared to other crystalline solids.

Zeolite can be considered as a special crystalline solid having a characteristic framework

structure with cavities occupied by ions and water molecules that have considerable freedom of
movement.
Zeolites are crystalline solids that are known to have well defined three dimensional structures
that contain micropores in them. The regular structural frameworks of zeolites are made up of
three primary components, namely oxygen, silicon, and aluminium. The micropores present in
their chemical structures are known to contain water and certain cations. The chemical structures
of zeolites feature a tetrahedral coordination between the aluminium atoms and the silicon atoms,
which is maintained with the help of the shared oxygen atoms. The structure of zeolites
(featuring a tetrahedral framework maintained by aluminium, silicon, and oxygen atoms) .
It can be noted that the composition of zeolites is similar to that of most clay minerals. For
example, both mineral clays and zeolites are known to be alumino-silicate compounds. However,
it is important to note that zeolites do not have the same crystal structures as most mineral clays.
For example, most mineral clays feature a layered crystal structure which has the ability to swell
(when water is absorbed) and shrink (when water is removed).
On the other hand, the crystalline structures of zeolites are known to be rigid in nature. These
structures are known to contain a network of tiny micropores that fall in between the tetrahedral
geometry. It can be noted this structure permits water to freely move in and out of these pores.
Since all the micropores present at the molecular level in zeolites have similar sizes, these
substances can also be employed as molecular sieves. Microporous zeolites can hold molecules
of water and certain positively charged ions such as the calcium cation and the potassium cation
within their pores.
Synthesis Of Zeolites
Zeolite synthesis is an active field of research because zeolites with uniform micropores are
important in many industrial processes in catalysis, adsorption and separation and are finding
new applications in electronics, magnetism, chemical sensors, medicine, etc. Since the
pioneering work by Barrer and Milton in the 1940s, there has been much progress during the last
60 years in the synthesis of zeolites. A large number of zeolites with new framework topologies,
compositions, and properties have been successfully prepared through continued synthetic
efforts. Up to now, thousands of zeolite materials have been prepared, which correspond to 174
structure types of zeolites (each being assigned a three-letter code by the Structure Commission
of the International Zeolite Association) Moreover, great improvements have been achieved in
zeolite synthesis in recent years, in particular, the synthesis of silica-based zeolite materials with
extra-large pores and interconnected channel systems, and the proper control of the sizes and
morphologies of zeolite crystals. All these developments are, in fact, attributed to innovations in
synthetic strategies as well as to the understanding of the crystallization process of zeolites.
Intense research activity in zeolite synthesis is shown by a growing body of literature, . the
hydrothermal synthesis of zeolite materials will be discussed along with the important factors
affecting the synthesis and some synthetic routes developed on the basis of conventional
hydrothermal synthetic technique. The methods of preparation of zeolites with different particle
sizes and morphologies will also be presented. The mechanistic aspects of zeolite synthesis are
outlined. Current improvements in zeolite synthesis are highlighted with emphasis on new
synthetic strategies, leading to many novel structures.

The zeolite Mineral species and structural group (Nickel-Strunz classification) includes:[4]
[11][37][38][39]
 09.GA. - Zeolites with T5O10 units (T = combined Si and Al) – the fibrous zeolites
o Natrolite framework
(NAT): gonnardite, natrolite, mesolite, paranatrolite, scolecite, tetranatrolite
o Edingtonite framework (EDI): edingtonite, kalborsite
o Thomsonite framework (THO): thomsonite-series
 09.GB. - Chains of single connected 4-membered rings
 o Analcime framework (ANA): analcime, leucite, pollucite, wairakite
o Laumontite (LAU), yugawaralite (YUG), goosecreekite (GOO), montesommaite (MO
N)
 09.GC. - Chains of doubly connected 4-membered rings
o Phillipsite framework (PHI): harmotome, phillipsite-series
o Gismondine framework (GIS): amicite, gismondine, garronite, gobbinsite
o Boggsite (BOG), merlinoite (MER), mazzite-series (MAZ), paulingite-series
(PAU), perlialite (Linde type L framework, zeolite L, LTL)
 09.GD. - Chains of 6-membered rings – tabular zeolites
o Chabazite framework (CHA): chabazite-series, herschelite, willhendersonite and SSZ-
13
o Faujasite framework (FAU): faujasite-series, Linde type X (zeolite X, X zeolites),
Linde type Y (zeolite Y, Y zeolites)
o Mordenite framework (MOR): maricopaite, mordenite
o Offretite–wenkite subgroup 09.GD.25 (Nickel–Strunz, 10
ed): offretite (OFF), wenkite (WEN)
o Bellbergite (TMA-E, Aiello and Barrer; framework type
EAB), bikitaite (BIK), erionite-series
(ERI), ferrierite (FER), gmelinite (GME), levyne-series (LEV), dachiardite-series
(DAC), epistilbite (EPI)
 09.GE. - Chains of T10O20 tetrahedra (T = combined Si and Al)
o Heulandite framework (HEU): clinoptilolite, heulandite-series
o Stilbite framework (STI): barrerite, stellerite, stilbite-series
o Brewsterite framework (BRE): brewsterite-series
 Others
o Cowlesite, pentasil (also known as ZSM-5, framework type MFI), tschernichite (beta
polymorph A, disordered framework, BEA), Linde type A framework (zeolite A,
LTA)

Applications.
 are three main uses for zeolites in industry, the most important being catalysis, but others
include gas separation and ion exchange:

 Catalysis

Zeolites are extremely useful as catalysts for several important reactions involving
organic molecules. The most important are cracking, isomerisation and hydrocarbon
synthesis. Zeolites can promote a diverse range of catalytic reactions including acid-base
and metal induced reactions. The reactions can take place within the pores of the zeolite -
which allows a greater degree of product control.

 Gas Separation

A widely used property of zeolites is that of gas separation. The porous structure of
zeolites can be used to "seive" molecules having certain dimensions and allow them to
enter the pores. This property can be fine tuned by variating the structure by changing the
 size and number of cations around the pores. Other applications that can take place within
the pore include polymerisation of semiconducting materials and conducting polymers to
produce materials having unusual physical and electrical attributes.

 Ion Exchange

Hydrated cations within the zeolite pores are bound loosely to the zeolite framework, and
can readily exchange with othercations when in aqueous media. Applications of this can
be seen in water softening devices, and the use of zeolites in detergents and soaps. It is
even possible to remove radioactive ions from contaminated water, as was demonstrated
at nuclear accidents at Chernobyl and at Three-Mile Island.

Catalytic cracking and the interconversion of aromatics by zeolites

The zeolite-based (Sections 14.15 and 24.12) heterogeneous catalysts play an important role in
the interconversion of hydrocarbons and the alkylation of aromatics as well as in oxidation and
reduction. Two important zeolites used for such reactions are faujasite (Fig 26.22), also known
as zeolite X or zeolite Y (the X or Y terminology is defined by the Si:Al ratio of the material, X
has a higher Al content) and zeolite ZSM-5, an aluminosilicate3.Explain the different methods to
prevent Corrosion .zeolite with a high Si content. The channels of ZSM-5 consist of a three-
dimensional maze of intersecting tunnels (Fig. 26.23). As with other aluminosilicate catalysts,
the Al sites are strongly acidic. The charge imbalance of Al3 in place of tetrahedrally
coordinated Si(IV) requires the presence of an added positive ion. When this ion is H+ (Fig.
26.24) the Brønsted acidity of the aluminosilicate can be higher than that of concentrated H2SO4
and is termed superacid (Section 4.15); the turnover frequency for hydrocarbon reactions at these
sites can be very high. Natural petroleum consists of only about 20 per cent of alkanes suitable
for use in petrol (gasoline) and diesel with chain lengths ranging from C5H12, pentane, to
C12H26. Conversion of the higher molar mass hydrocarbons to the valuable lighter ones
involves breaking the C-C bonds but also structural rearrangement of the hydrocarbons through
dehydrogenation, isomerization, and aromatization reactions. All these processes are catalysed
by a solid acid catalyst based on alumina, silica, and zeolites. Acidic clays and mixed
Al2O3/SiO2 were originally used for this process in the 1940s but since the 1960s these
catalysts have been largely superseded by zeolites. The principal zeolite used for catalytic
cracking is zeolite Y, in which the extra-framework cations have been replaced with lanthanoid
ions, typically a mixture of La, Ce, and Nd. The mechanism of the catalytic cracking initially
involves protonation of the alkane or alkene chain by the Brønsted acid sites in the zeolite pores
followed by cleavage of the C-C bond in the beta-position to the C atom carrying the positive
charge.
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide.
It is the gradual destruction of materials (usually a metal) by chemical or electrochemical
reaction with their environment. Corrosion engineering is the field dedicated to controlling and
preventing corrosion.

BARRIER Method

One of the easiest and cheapest ways to prevent corrosion is to use barrier coatings like paint,
plastic, or powder. Powders, including epoxy, nylon, and urethane, adhere to the metal surface to
create a thin film. Plastic and waxes are often sprayed onto metal surfaces. Paint acts as a coating
to protect the metal surface from the electrochemical charge that comes from corrosive
compounds. Today’s paint systems are a combination of different paint layers that serve different
functions. The primer coat acts as an inhibitor, the intermediate coat adds to the paint’s overall
thickness, and the finish coat provides resistance to environmental factors.

The biggest drawback with coatings is that they often need to be stripped and reapplied. Coatings
that aren’t applied properly can quickly fail and lead to increased levels of corrosion. Coatings
contain volatile organic compounds, which make them hazardous to people and the environment.

HOT -Dip Galvanization Method

This corrosion prevention method involves dipping steel into molten zinc. The iron in the steel
reacts with the zinc to create a tightly bonded alloy coating which serves as protection. The
process has been around for more than 250 years and has been used for corrosion protection of
things like artistic sculptures and playground equipment.

Unfortunately, galvanization can’t be done on-site, meaning companies must pull equipment out

of work to be treated. Some equipment may simply be too large for the process, forcing
companies to abandon the idea altogether. In addition, zinc can chip or peel. And high exposure
to environmental elements can speed up the process of zinc wear, leading to increased
maintenance. Lastly, the zinc fumes that release from the galvanizing process are highly toxic

Alloyed Steel
Alloyed steel is one of the most effective corrosion prevention methods around, combining the
properties of various metals to provide added strength and resistance to the resulting product.
Corrosion-resistant nickel, for example, combined with oxidation-resistant chromium results in
an alloy that can be used in oxidized and reduced chemical environments. Different alloys
provide resistance to different conditions, giving companies greater flexibility.

Despite its effectiveness, alloyed steel is very expensive.

Cathodic protection
Cathodic protection protects by electrochemical means. To prevent corrosion, the active sites on
the metal surface are converted to passive sites by providing electrons from another source,
typically with galvanic anodes attached on or near the surface. Metals used for anodes include
aluminum, magnesium, or zinc.

While cathodic protection is highly effective, anodes get used up and need to be checked and/or
replaced often which can drive up costs of maintenance. They also increase the weight of the
attached structure and aren’t always effective in high-resistivity environments

EONCOAT- A new method.

EonCoat is a cost-effective, maintenance-free, and easily applied solution which protects the life
of the asset. It works by a combination of the above methods. First, it alloys the metal, then
provides a thick layer of inhibitors that will repair any damage to the alloy layer. EonCoat uses
no toxic chemicals and has no VOC’s so it is the most environmentally friendly solution.
Independent testing shows this solution to be the most effective and long-lasting of all the
alternatives. The 30-year warranty ensures your equipment stays protected.

References
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