Graphite and Fullerenes

Introduction to Graphite
Graphite originated from the Greek term graphene, which means
"writing," and its name comes from the fact that it was originally used
to make pencils. It is a carbon allotrope that is grey in colour and opaque.
It is recovered from the earth, but its formation takes years.
In the meanwhile, the highest source of graphite is in China. As it is made
up of carbon atoms, graphite is a non-metal. One of its properties,
however, causes it to behave like a metal. Graphite is favoured by high
pressure and high temperature, and it is the most stable form of carbon.
Diamond will tend to change to graphite under these normal Figure 1 Graphite

circumstances.
Graphite is a half-metal and a kind of crystal carbon, as well as one of the most well-known
carbon allotropes. It would be among the most robust forms of carbon accessible under perfect
conditions. To establish a standard temperature for the production of carbon compounds.
However, because the process requires millions of years, graphite is a significantly more
durable form of carbon than diamond under these regular standard settings. Yeah. If it is burned
in the open air, carbon dioxide gas is produced. With a density of 2.09–2.23 g/cm3, graphite is
an excellent heat and electrical conductor.
Accidental Production of Graphite
Edward G. Acheson accidentally produced graphite for the first time while working on a high-
temperature carborundum experiment. He discovered that at roughly 4150 oC, the silicon in
carborundum vaporises, leaving the carbon in graphite form behind.

Schematic diagram of Arc discharge method for the synthesis of graphite from silica
carborundum.
In 1896, he was given a patent for graphite fabrication, and commercial production of the
material began in 1897. Graphite is a carbon allotrope, neither an element nor a combination.
It doesn't have its own chemical formula.
Structure of Graphite
Graphite is a carbon allotrope. Each carbon atom in
graphite is joined to three other carbon atoms by a single
covalent bond, forming a hexagonal ring that is organized
in a layer. In general, graphite is employed as an
electrode in pencil batteries. It has a structure that is made
up of two-dimensional layers. A sandwich-like structure
is another name for it. Each carbon atom is SP to
hybridize in graphite's structure, and hexagons are
grouped in layers. Each carbon atom in the layer is
bonded to three other carbon atoms in the same plane via
covalent bonds. Weak wall forces between two layers
satisfy the 4th valence of the carbon atom. A single sheet Figure 2. Structure of Graphite
of graphite is known as graphene.
Properties of Graphite
Graphite is a carbon allotrope that is used in nuclear power reactors to make moderator rods.
The following are its characteristics: Graphite can be found in its natural condition or
manufactured artificially.
• It's an opaque greyish black material.
• Smooth and slippery to the touch, lighter than diamond.
• It is a good heat and electrical conductor.
• The sp2 hybridization of carbon atoms occurs.
• It's a crystalline substance.
• It melts at around 1800 degrees Fahrenheit.
• Non-inflammable in nature
• Vander Waal forces are weak, therefore it's soft
Conducting Nature of Graphite
In graphite, each carbon atom is only covalently bonded
to three other carbon atoms, rather than to four as in
diamond. Graphite contains layers of carbon atoms. The
layers slide over each other easily because there are only
weak forces between them, making graphite slippery.
Graphite contains delocalised electrons (free electrons).
These electrons can move through the graphite, carrying
charge from place to place and allowing graphite to
conduct electricity.
Types of Graphite
Natural Graphite (β form)
Natural graphite is a graphitic carbon mineral that is a good heat and electrical conductor. With
a melting point of roughly 3650°C, it is stable across a wide temperature range. Natural graphite
comes in three varieties: High crystalline content, Amorphous, and Flake. This form is also
known as β form and it is hexagonal form.
Synthetic Graphite (α form)
Coke and pith are used to make synthetic graphite. In comparison to the natural one, it is less
crystalline. Synthetic graphites are divided into two categories. The first is electro graphite,
which is pure carbon created in an electric furnace from coal tar pitch and calcined petroleum
coke. The second is synthetic graphite, which is made by heating calcined petroleum pitch to a
temperature of 28000°C. This form is also known as α form and it is rhombohedral in nature.
Uses of Graphite
• The mineral graphite is used to make pencil lead.
• Because of its capacity to absorb fast-moving neutrons, graphite is employed in nuclear
reactors to regulate the nuclear fission reaction.
• Graphite is utilised as a lubricant in machine components due to its slippery nature.
• Because of its free electrons, graphite is employed as heat and electrical conductors in
a variety of operations.
• Graphite is employed in high-temperature applications such as phosphorus and calcium
carbide manufacturing.
• In aqueous electrolytic processes, such as the synthesis of halogens, graphite is utilised
as an anode.
• As a carbon brush, graphite is employed as an electrical substance in electric motors.
• Crucibles are made from it because of its chemical resistance and high melting
temperatures.
• For lithium-ion batteries, graphite materials are employed as the anode material.
Applications of Graphite
Chemical Manufacturing
Graphite is employed in many hot areas in the chemical industry, such as in the manufacturing
of phosphorus and calcium carbide in arc furnaces. In some electrolytic processes in liquids,
such as halogen synthesis, graphite is utilised as an anode (chlorine and fluorine).
The Nuclear Power Industry
In nuclear reactors, large amounts of high-purity electro graphite are utilised to make
presidential sticks and display components. The lowest neutron absorption results in the
formation of electro graphite with high thermal conductivity, high strength, and high
temperatures.
Applications of Electricity
Carbon brushes in electric motors include a significant quantity of graphite, which is employed
as an electrical substance. The distance and structure have a big impact on a component's
service life and performance.
Applications in Mechanical Engineering
Piston rings, thrust bearings, journal bearings, and vanes are all examples of when graphite is
employed as an engineering material. Carbon-based seals can be found in gasoline pumps and
on the engine walls of a variety of aviation engines.
Introduction to Fullerenes
Fullerenes are fourth allotropic form of carbon. In comparison with graphite and diamond with
extended solid-state structures, fullerenes are spherical molecules which have solubility in
various organic solvents. This property can be used for different chemical manipulation.
Discovery of Fullerenes
Fullerene is a carbon cage structure having fused ring system which consists of pentagons and
hexagons.
The first proposal of buckyball was given by Eiji Osawa, Japan. He recognized that
corannulene, a cyclopentane ring fused with 5 benzene rings was a part of football framework
and hypothesized that entire structure could exist.
In 1985, the group of scientists Richard Smalley, Robert Curl, James Heath, Sean O'Brien, and
Harold Kroto synthesized the first fullerene molecule, buckminsterfullerene (C60) at Rice
University. These scientists named newly discovered molecule in honor of architect R.
Buckminster Fuller who created geodesic dome with same shape.

Structure of Fullerenes
Fullerenes are composed of fused hexagons and pentagons. C60 and C70 are most accessible
members of this family. The high symmetry found in this molecule is an important property.
The electronic structure of fullerenes is a very critical
factor which determines their exceptional chemical
properties. Each carbon atom of a fullerene is linked to
three neighbouring carbon atoms on the vertex of a
polyhedron; therefore it forms two single bonds and one
double bond. There are two types of bonds in a C60
fullerene namely; a bond shared between a hexagon and
pentagon which behaves like single bond and that which
is shared between two hexagon which behaves like a
double bond. The hybridization of C in fullerene ranges
from sp2 to sp3 as we move from lower carbon number
to the higher carbon number. Figure 3 Fullerene derivatives
Example: Structure of C60 fullerene.
C60 molecule is composed of 60 carbon atoms which are arranged as 12 pentagons and 20
hexagons. All rings are fused and double bonds are highly conjugated. The reason for high
symmetry of this molecule is 120 symmetrical operations found in molecule like rotation
around the axis and reflection in plane which maps the molecule onto itself. When a carbon
atom is placed at each vertex of molecule which all valences satisfied by two single bonds and
one double bond, stabilized by resonance gives structure of C60 molecule, appears to be
aromatic. Other forms of fullerene are Fullerane which is fully saturated fullerene (example,
the hydrocarbon C60H60) and Fulleroids are fullerene-like compounds as they resemble
fullerenes in structure but do not confirm the definition of a fullerene (example,
Heterofullerens, Norfulleres, Homofullerene, Secofullerene).

Synthesis of Fullerenes
1. Synthesis by Laser Vaporization of Carbon
In this method fullerenes are produced in a supersonic expansion nozzle by a pulsed laser which
is focused on a graphite target in an inert atmosphere (helium). This process involves
vaporizing carbon from a rotating solid disc of graphite into a high-density helium flow using
a focused pulsed laser
2. Synthesis by Electric arc Heating of Graphite
This method was conceptualized by Kratchmer and Huttman in 1990. The process involves
generating an electric arc between graphite rods in an inert atmosphere which produces a fluffy
condensate (Soot). A fraction of this fluffy condensate contains the toluene extractible
fullerenes. The fullerenes in the soot
are then extracted by solvation in a small amount of toluene after extraction the toluene
(solvent) is removed using a rotary evaporator and the solid mixture made up of mostly C60
with small amount of higher fullerenes is subjected to liquid chromatography Process to obtain
pure C60

Synthesis by Electric arc Heating of Graphite

Properties of Fullerene
Physical Properties of Fullerene
1) Fullerene shows variation in behaviour and structure on changing the temperature. At a
higher temperature, the fullerene is converted into the C70 form.
2) Fullerene shows the change in the structure under different pressures.
3) The ionization enthalpy of fullerene is 7.61 electron volts.
4) The electron affinity of fullerene is 2.6 to 2.8 electrons volts.
Chemical Properties of Fullerene
1) Fullerene (C60) resembles an electrophile in chemical reactions.
2) Fullerene can act as an electron acceptor group. It can easily accept three electrons or
more. Therefore, it can behave as an oxidizing agent.
3) Fullerenes are doped with alkali or alkaline earth metals so that they can exhibit
superconductivity properties.
4) Ferromagnetism is a property of fullerene.
5) Carbon molecules abound in fullerene. As a result, it's very soluble in organic solvents.
Applications and Examples
Fullerene molecules can be used for drug delivery into the body, as lubricants, as catalysts
and in the form of carbon nanotubes can be used for reinforcing composite materials, eg
sports equipment like tennis rackets. They have many chemical synthetic and pharmaceutical
applications. They may be use as vehicles to carry drugs into cells, the cage like fullerene
molecules could contain a drug, and the combination can pass easily through the wall of a target
cell.
Chemical derivatives of fullerenes have fascinating electrical and magnetic behaviour
including superconductivity and ferromagnetism. C60 is an optical limiter. When light is
shone on it, a solution of fullerene-60 turns darker instantly and the more intense the light, the
darker it gets, so the intensity of transmitted light is limited to a maximum value. This limiting
light transmittance property can be used in the design of safety goggles in intense light
situations e.g. people working with laser beams.
Fullerenes may used in certain medical applications – nanomedicine.
The idea is to use the very small fullerene molecules to easily deliver drugs directly into cells
in a highly controlled manner. This is possible because the extremely small diameter of the
nanoparticle fullerenes (which act like a cage to hold the drug) allows them to readily pass
through cell membranes.
Fullerenes are being developed that have excellent lubricating properties
These lubricants significantly reduce friction in moving metal parts of machines from cog
wheels to ball bearings and maybe artificial joints after orthopedic operations on hips and
knees!