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Pilkington
Lecture 29 Group 14
1
Lead is the oldest metal known. The book of Job, probably written in 400 B.C.
has its author wishing to have his devotion to God be recorded forever with an
iron pen and lead.
Lead was easy to hammer into sheets for writing and flooring materials, into
vessels for cooking and storing foods, and into pipes for plumbing.
Lead pipes were the original plumbing materials (some lead pipes still in service
have the insignia of Roman Emperors on them).
Both words plumbing and plumber are derived from the same Latin word plumbum
for lead. This is also the origin of the symbol Pb for the element.
Silicon and Germanium
Glass of which silicon in the form of silica is a prime component has been known
since about 1500 B.C.
In 1824 Berzelius isolated amorphous Silicon where others before him had
failed.
He named his new compound silicium from the Latin silex for flint a major
source of silica.
The name silicon was proposed in 1831 with the suffix on replacing ium to
establish a parallel with boron and carbon.
2
3. Allotropes of C and Si
Diamond and Graphite
Diamond and graphite are allotropes of carbon i.e. different forms of the
same element.
Graphite is metallic in appearance, whereas diamond is transparent and one of
the hardest substances known.
The diamond structure is a 3-dimensional covalent network crystal composed of
interconnected C-C single bonds (remember the unit cell is similar to Zinc blende
accept that all the spheres represent carbon instead of alternating between Zn
and S.
Natural diamonds are not easy to come by and formed in rock melts and
temperatures in excess of 14000C.
Synthetic diamonds are made in small grit sizes and used for various grinding
applications.
Gem-quality diamonds can be made but are not as costly as the natural variety.
The custom of giving a diamond engagement ring seems to have been started by
the Venetians toward the end of the 15th Century.
Imitation diamonds are yttrium-aluminium garnet, strontium titanate, or cubic
zirconia, ZrSiO4.
3
Graphite is a layered structure characterized by strong pp-pp bonding within
each layer and only London (van der Waals) forces between them.
The relative strength of these two different types of interactions is reflected
in the C-C distances.
The soft and lubricating properties of graphite are due to these layers being
able to easily slide by each other.
Pencil lead is also graphite (mixed with clay). Pressure on the pencil head causes
the layers of graphite to rub off on a piece of paper.
Charcoal and soot are very tiny particles of graphite. The large surface areas of
these materials make them useful for adsorbing various gases and solutes.
-bonding in graphite
Every C bonded to 3 others
Buckminsterfullerine C60
In 1985 Harry Kroto, Richard Smalley and Robert Curl produced an amazing
third allotrope of carbon.
They found that when graphite was vaporized by a laser, a variety of large
clusters and even numbers of carbon atoms are formed.
One of the most prevalent of these was C60.
The structure remained a mystery and two shapes came into mind:
(a) The geodesic domes of the American architect R. Buckminster Fuller and.
(b) The shape of the European football or an American soccer ball.
4
Buckminster Fuller's Dome - Expo '67 Montreal
Since their discovery in the mid 1980s an incredible variety of fullerenes have
been produced and characterized. Each is best thought of as 12 pentagons and a
varing number of hexagens.
As a result of these discoveries, Kroto, Smalley and Curl received the Nobel
Prize in chemistry.
5
C60-Fullerene at 153 deg.K. C60 crystallizes in a face centered cubic
arrangement.
Carbon Nanotubes
In 1991, Sumio Iijima made still another discovery involving carbon allotropes.
He produced long cylindrical (10-30 nm in diameter) multiwalled, tubelike structures with
hemispherical end caps.
Given their dimensions, they quickly became known as nanotubes.
A short time later, Thomas Ebbesen and Pulickel Ajayan, from Iijima's lab, showed how
nanotubes could be produced in bulk quantities by varying the arc-evaporation conditions.
This paved the way to an explosion of research into the physical and chemical properties of
carbon nanotubes in laboratories all over the world.
Nanotubes, depending on their structure, can be metals or semiconductors. They are also
extremely strong materials and have good thermal conductivity. The above characteristics
have generated strong interest in their possible use in nano-electronic and nano-mechanical
devices. For example, they can be used as nano-wires or as active components in electronic
While normally nanotubes are straight, ways have been devised to prepare them in a ring
form.
6
Nanotube Rings
The rings are composed of many layers of single-walled nanotubes, and have a radius of
typically 0.7 micron.
Coiling has been observed in proteins and other biomolecules, where hydrogen bonding is
thought to provide the main force for coiling. Carbon nanotubes however present a novel
behavior where coiling involves only van der Waals forces.
The rings, which we can position on metal electrodes, allow us to study novel electric
transport phenomena. Shown below is an AFM micrograph of a one micron-diameter ring
(the purple circle) placed over gold electrodes (the light blue objects).
SEM (Scanning
Electron Microscope)
image of nanotube
rings on a silicon
substrate. The image
is magnified 8000
The nanotubes used to form the times.
rings are extremely small; their
diameter is only 1.4 nm. They are 1-
dimensional conductors and at low
temperatures,
They have a tensile strength (ability to oppose rupture under tension) some 50-
100 times that of steel at one-sixth of the weight.
This makes them candidates for a large number of applications and uses.
The tubes can be fashioned into a variety of fibers, ropes, and cables which will
be put to great use in the next generation of high strength fibers stuffer yet
less brittle than their graphite relatives.
Tennis rackets, golf clubs or fishing rods could be made out of these materials.
Single walled nanotubes have unique electronic properties. They can conduct
electricity as easy as a metal so in the future, they could rival copper wires but
be more flexible and lighter.
7
In contrast Silicon
One allotrope; diamond structure where every Silicon is tetrahedrally bonded to 4
others.
Silica cannot undergo p-p bonding so there are no forms similar to graphite or
buckyballs.
3. Me2CO O
CH3CCH3 and p-p bonds
acetone
Me2SiO Si-O-Si-O-Si-O
8
4. (SiH3)3N: Planar
Si
CH3
resembles the ammonia molecule
H3C NH3
CH3
sp3 hybridized
C does not
have d orbitals so
cannot bond like Si
The p-d bond is an example of a DATIVE bond both electrons come from the
same element.
The 3d orbitals decrease in size from left to right (because of effective nuclear
charge).
The overlap of N (2p orbitals) and Si (3d orbitals) is good enough and favorable
to allow for the planar shape.