4 .

3 c O val e N T S T r u c Tu r e S

aotops
Allotropes o the same element can vary in both physical and chemical
Dfnition o otops
properties. As described by IUPAC,
otops are diferent
C arbon is one o the most ascinating elements in the periodic table,
structural modications o the
and lie orms on Earth are based on carbon. C arbon has a number o
same element.
allotropes: graphite, diamond, graphene, and C 60 ullerene.

Covalent network solids

 Graphite, diamond, and graphene are examples o covalent
network solids. A covalent network solid is one in which the
atoms are held together by covalent bonds in a giant three-
dimensional lattice structure ( in large networks or chains) . Another
well known example o a covalent network solid is quartz, which is
silicon dioxide, S iO 2 .
 In contrast, C 60 ullerene is molecular.

Graphite
Graphite is an example o a covalent network solid. In graphite there
are layers o hexagonal rings consisting o carbon atoms. These layers
are connected by weak intermolecular orces o attraction, which are
called London orces, leading to the use o graphite as a lubricant
and in pencils ( the so- called lead in our pencils is not lead but carbon
in the orm o graphite) . E ach carbon atom adopts a trigonal planar
geometry, and is covalently bonded to three other each carbon atoms
Poptis o ont
at a bond angle o 1 2 0. The coordination number o each carbon
is three in the structure. Although the covalent bonds are strong ntwok soids
within the sheets, the London orces between the layers are weak,  Melting points. Covalent
which allows the layers to slide past each other, and thus graphite network solids have high
can be used as a lubricant ( fgure 1 3 ) . Unlike other covalent network melting points (typically
solids, graphite is a good conductor o electricity as it has delocalized greater than 1000 C and
 electrons. much higher than the
melting points o molecular
substances).
 Electrical conductivity.
Covalent network solids are
poor electrical conductors
(though graphite and
graphene are clear
exceptions  electrical
conductivity is one o the
characteristics that makes
graphene remarkable) .
 Solubility. They are typically
insoluble in common solvents.
 Hardness. Generally, covalent
network solids are hard,
Figure 13 Graphite is a covalent network solid that consists of hexagonal layers of carbon though in graphite the layers
atoms, which can slide past each other. The layers are connected by weak intermolecular can slide past one another.
forces of attraction (London forces)

117
4 C H E M I C AL B O N D I N G AN D S T R U C T U R E
Figure 14 Diamond is an allotrope of carbon
with a covalent network lattice structure.
Large crystals of diamond are mined for use
as gemstones. Small crystals are used as an
industrial abrasive. High-quality crystals of
diamond are found in South Africa, Russia,
Brazil, and Sierra Leone.
International
perspective
Throughout history diamonds
have oten been a potential
source o signicant global
confict. The term blood
diamond has been coined
to describe diamonds mined
in regions o confict and
subsequently sold to und such
conficts. What responsibilities
do nations and governments
have in the import o products
such as gemstones and precious
metals?
usefl resorce
Look at the history o the
discovery o graphene and
current research developments
in using this material at the
University o Manchester, UK,
the university where Geim and
Novoselov did their research to
win the Nobel prize in Physics
in 2010, http://www.graphene.
manchester.ac.uk/story/
118
Diamond
D iamond is also a covalent network solid. In the lattice structure o
diamond, each carbon atom is covalently bonded to our other carbon
atoms in a tetrahedral arrangement, with a C C C bond angle o 1 09.5 
( fgure 1 4) . The coordination number o each carbon within diamond is
our. D iamond is one o the hardest substances known because o this
covalently bonded interlocking structural arrangement o tetrahedra. For
this reason diamond is oten used in heavy- duty cutting tools such as
saws, polishing tools, and dental drills.
The melting and boiling points o diamond are very high ( 3 5 5 0 and
482 7 C , respectively) . Unlike graphite, in diamond the valence electrons
are localized in the single  covalent bonds, and thereore cannot move
reely. This means diamond does not conduct electricity.
S trong covalent bonds in diamond make it is insoluble in all common
solvents.
Diamonds are forever?
It has been said that diamonds are a girls best riend, but have you
ever considered i diamonds last orever?
Unortunately not! Under ambient conditions, diamond is
thermodynamically unstable and eventually turns into another allotrope
o carbon, graphite. However, at room temperature this process is
extremely slow, so diamond is said to be kinetically stable. At 1 000 C
the conversion o diamond into graphite accelerates and at 1 700 C it
completes within seconds. When we talk about stability in chemistry we
need to consider both thermodynamic stability and kinetic stability.
Graphene  the super material!
Graphene is not only one o the thinnest and strongest o known
materials, but it is also the frst two- dimensional crystal ever discovered.
Graphene is a covalent network solid, but diers rom graphite in that it
consists o a single planar sheet o carbon atoms arranged hexagonally
( fgure 1 5 ) , and is only one atom in thickness. As in graphite, each
carbon atom is covalently bonded to three other carbon atoms so the
coordination number o each carbon in graphene is three. The carbon
atoms are densely packed in a honeycomb crystalline lattice, but the
lattice is actually planar, which makes it remarkable as a crystalline
structure.
The experimental evidence or the existence o graphene was obtained
in 2 004 by the Russian scientists Andre Geim and Konstantin Novoselov,
who won the Nobel Prize in Physics in 2 01 0 or their ground- breaking
experiments at the University o Manchester in the UK.
Graphene is an excellent thermal and electrical conductor, 3 00 times
more efcient than copper. A piece o graphite 1 mm thick consists o
three million sheets o graphene, with one stacked on top o another.
When graphite is prised apart it becomes essentially graphene. I a
 4 . 3 c O val e N T S T r u c Tu r e S

graphene sheet is rolled up, it orms a carbon nanotube (sub-topic A.6) .

When this, in turn, is olded up into a sphere it becomes a fullerene,
which looks like a soccer ball (discussed below) .
Graphene is a remarkable material, especially because o its superb
electrical conductivity, strength, fexibility, and transparency.
Graphene has been described as the new silicon . S ome o the uture
applications o graphene lie in the ollowing research areas:
 development o grapheneplastic composite materials to replace
metals used in the aerospace industry because o their low density
and high strength
 liquid- crystal displays ( LC D ) and fexible touch- screens or mobile
devices due to the fexibility, transparency, and electrical conductivity
o graphene.
Ater the discovery o graphene in 2004 a whole class o two- dimensional
materials have emerged, which include the single layers o boron nitride,
B N and molybdenum disulde, MoS 2 . B N is an excellent lubricant and can Figure 15 Graphene
be used in a vacuum so it is important in space research and is also used in
ceramic materials. MoS 2 is also a very good lubricant.
atiity
C60 fullerene
gphn nnoibbons - th
In 1 985 a new orm o carbon allotrope called ullerene, with carbon t ndmk in th fd o
atoms arranged in closed shells, was discovered by Robert F. C url Jr phn!
(working at Rice University in the USA) , S ir Harold W. Kroto ( working
at S ussex University in the UK) , and Richard E. Smalley ( also working Find out about graphene
at Rice University) . In 1 996 these scientists were awarded the Nobel nanoribbons (GNRs) by
Prize in C hemistry or their discovery o ullerenes. The number o accessing the chemical
carbon atoms in the shell was ound to vary, which led to the discovery literature or online and why are
o several new carbon structures. Fullerenes were ound to orm when material scientists so excited
vaporized carbon condensed in an atmosphere o an inert gas. C lusters about their future development.
o C 70 and C 60 were initially synthesized, with more C 60 than C 70 clusters
being ormed. The structure o each C 60 molecule was ound to consist o
a truncated icosahedral cage, which has the shape o a soccer ball. The
spherically symmetrical C 60 molecule was unique in nature at its time o
discovery.
In the C 60 polyhedron cage there are 2 0 hexagonal suraces and
1 2  pentagonal suraces, and each carbon atom is covalently bonded
to three others so that the coordination number is three, but the
arrangement is not planar ( gure 1 6) .
The geodesic dome designed by the US architect R. B uckminster
Fuller or the 1 96 7 Montreal Wo rld E xhibition in C anada
has this shap e o a so ccer ball and hence C 60 has been named
bu ckm insterfullerene. These spherical ullerenes are sometimes
reerred to as buckyb alls. Figure 16 Molecular structure of c6 0
n (bkminstn) ,
C 60 ullerene is not a covalent network solid, and so is dierent rom showing 60 carbon atoms arranged
graphite, diamond, and graphene. C 60 is composed o individual in a spherical structure that consists
molecules with strong covalent bonds, but with weak London orces of interlinking hexagonal and
between the molecules. pentagonal rings, like a soccer ball

119
4 C H E M I C AL B O N D I N G AN D S T R U C T U R E
Figure 17 Structure o quartz, which is a
crystalline orm o silicon dioxide, SiO 2 .
Crystals o quartz are used in optical and
scientifc instruments and in electronics, such
in as quartz watches
Fullerenes are black solids that do not dissolve in water, but can dissolve
in some non-polar solvents (or example, benzene) . In organic solvents
they orm coloured solutions; the colour depends on the solvent
and varies rom red to brown to magenta. C 60 , unlike both graphite
and graphene, does not conduct electricity. Although it does contain
delocalized electrons, the electrons do not have the capacity to move rom
one C 60 molecule to the next because o the symmetrical nature o C 60 .
Many new compounds o ullerenes have been synthesized subsequently,
with atoms or small molecules enclosed within the ullerene cage. Such
inclusion complexes can potentially be used as gene and drug carriers;
other applications lie in the areas o superconductivity and erromagnetism
because o the unusual electromagnetic properties o inclusion complexes.
Fullerenes also have the ability to ft inside the hydrophobic cavity that
orms the active site o the human immunodefciency virus (HIV) protease
enzymes and thereby inhibit them.
C arbon nanotubes are tube- shaped molecules, closely related to C 60 ,
and have electrical conductivity approximately ten times better than
copper and are 1 00 times stronger than steel. They are also used in
many electronic applications, replacing silicon, and in the synthesis o
new compounds that allow unstable substances to become stabilized
when incorporated within the tubes. The diameter o such tubes is
extremely small, in the order o 1 0 9 mm, on the nano scale. B uckyballs
and carbon nanotubes have become a vibrant and dynamic area o
chemical research in materials science, with numerous applications.
Serendipitous discoveries
The accidental discovery o buckminsterullerene is a classic example
o the importance o in chemistry. C arry out some research
in the library and online to fnd out how buckminsterullerene was
discovered. What other examples o serendipitous discoveries are
amous in chemistry?
Silicon dioxide, SiO 2 (quartz)
S ilicon dioxide, S iO 2 , oten called silica, is ound in its amorp hous orm
( that is, a solid with no ordered structure) as sand. In its most common
crystalline orm it is called quartz. Quartz is another example o a
three- dimensional covalent network solid. It consists o arrays o S iO 4
tetrahedra arranged in a lattice (fgure 1 7) . E ach silicon atom is bonded
covalently to our oxygen atoms and each oxygen atom is bonded
covalently to two silicon atoms. The SiOS i geometrical arrangement
is bent because o the presence o two non- bonding pairs o electrons
on each oxygen atom. Silicon dioxide has both a high melting point
( 1 71 0 C ) and a high boiling point (2 2 30 C ) due to the existence o
strong covalent bonds.
B oth crystalline and amorphous dioxide are insoluble in water and solid
crystalline SiO 2 does not conduct electricity (since there are no delocalized
electrons present) or heat. Note that molten silicon dioxide can conduct
electricity however as electrons are ree to move in the molten state.