Carbon and Its Allotropes

Susan Evans
Chemistry 405
April 30, 2001
Carbon, element six on the periodic table and having the symbol C, is the
fundamental building block of all living organisms. Thus, all carbon-containing
compounds are known as organic compounds. Excluding hydrogen, carbon is able to
form more compounds than any other element. [Carbon] is the major component of
coal, petroleum, asphalt, limestone, and most materials made by plants and
animals.(Carbon, Encarta Online, 2001) Most natural and synthetic fibers contain
carbon. Building materials such as wood and plastics, heat and energy sources such as
natural gas and coal, pesticides, medicines, and many foods are composed in small or
large part of carbon. Carbon atoms from part or all of the backbone for the major
molecules of all living things on Earth, including sugars, proteins, fats, and
deoxyribonucleic acids (DNA).(Carbon, Encarta Online, 2001) In industry carbon
is used to make steel from iron, purify metals, and add strength to rubber.

In 1961 the international unions of physicists and chemists agreed to use the mass of the
isotope carbon-12 as the basis for atomic weight.(Carbon, Encarta 2000) Carbon-12, carbon13, and carbon-14 are the three isotopes of carbon that can be found in nature. Carbon-12 is the
most abundant isotope, accounting for about 98.89% of all carbon.(Carbon, Encarta Online,
2001) Although less plentiful, carbon-13 and carbon-14 have important uses. The nucleus of
carbon-13 is magnetic, which allows scientists to identify carbon-13 nuclei using nuclear
magnetic resonance. This technique enables them to study the structure of molecules containing
this isotope of carbon. Carbon-14 is radioactive with a half-life of 5730 years. This property of
carbon-14 lends itself to a technique called carbon dating, which is used to determine the age of
fossils, among other things. While an organism is alive, it contains a ratio of one atom of
carbon-14 for every 1012 atoms of carbon-12. When an organism dies, no additional carbon-14
is taken in. Carbon-14 decreases with time, so by measuring the carbon-12 - carbon-14 ratio, the
approximate date of death can be determined.
Four allotropes of carbon have been determined. Allotropes differ in the way the
atoms bond with each other and array themselves into a structure. Because of their different
structures, allotropes have different physical and chemical properties.(Carbon, Encarta
Online, 2001) Carbon exists as diamond, graphite, amorphous carbon, and the recently
discovered buckminsterfullerene. Each allotrope of carbon will be discussed in this paper, with
particular emphasis on diamond and graphite.
The structure and bonding in graphite lends itself to the properties that make it a good
lubricant, among other uses, which will be visited later. In graphite, the atoms form planar, or
flat, layers. Each layer is made up of rings containing six carbon atoms. Each atom has three
sigma bonds and belongs to three neighboring rings. The fourth electron of each atom becomes
part of an extensive pi bond system.(Carbon, Encarta Online, 2001) A structural diagram of
graphite is shown below, in Figure 1.

The free movement of pi bonds throughout the molecule enable graphite to

conduct electricity. Bonds between atoms within a layer of graphite are strong, but
the forces between the layers are weak.(Carbon, Encarta Online, 2001) Because of
this inter-layer weakness, the layers are able to move past each other giving rise to one
of graphites physical properties, softness. It is precisely this property that makes
graphite a good lubricant, alone or mixed with grease, oil, or water. The layers in
graphite can be easily removed. To see this, all one must do is write with a
pencil. The lead in a pencil is not actually lead, but a graphite-clay mixture.
Graphite has many uses other than those previously mentioned. Graphite is used as
electrodes in electrochemical industries where corrosive gases are given off, and for electric
furnaces that reach extremely high temperatures.(Graphite, Encarta Online, 2001) Graphite
can be used in these high-temperature furnaces because is it a poor conductor of heat. Graphite
is also used in high-temperature crucibles, some paints, and as a moderator in atomic
reactors. Because of the many uses of graphite, a method has been created for making the
allotrope in the laboratory. Graphite is made artificially by baking a mixture of petroleum coke

and coal tar pitch at 9500C (17400F) for 11 to 13 weeks, then transferring the baked product to
electric graphitizing furnaces and heating it to about 28000C (56000F) for 4 to 5
weeks.(Graphite, Encarta Online, 2001)
Graphite is the most stable allotrope of carbon. The other most widely-used allotrope of
carbon, diamond, is continuously undergoing a reaction into graphite. Fortunately, the process is
very slow. A faster method of converting graphite to diamond is used by diamond
makers. Extremely high pressure (more than 100,000 times the atmospheric pressure at sea
level) and temperature (about 30000C or 50000F) [are applied to graphite]. High temperatures
break the strong bonds in graphite so that the atoms can rearrange themselves into a diamond
lattice. About 90% of the diamonds used in tools in the United States are made this
way.(Carbon, Encarta Online, 2001) Diamonds of gem quality have been created, but the
best diamonds are found in nature.
The structure of diamond is quite different from that of graphite, giving rise to their many
differences. In diamond, each carbon atom bonds tetrahedrally to four other carbon atoms to
form a three-dimensional lattice. The shared electron pairs are held tightly in sigma bonds
between adjacent atoms.(Carbon, Encarta Online, 2001) The diamond structure is shown
in Figure 1. Diamond is rather inert and reacts with few chemicals this is due to its compact
crystal lattice. Diamond doesnt react with chemical reagents like acids and alkalis. However,
diamond reacts with sodium carbonate at high temperatures to form carbon
monoxide.(Crystalline Allotropes of Carbon, 2000)
Diamond is the hardest substance, four times harder than the next hardest natural
mineral, corundum.(The Mineral Diamond, 1996) It defines the upper limit of the Mohs
hardness scale, having a value of 10. Sought-after diamonds are colorless, but some rare
diamonds can be green, blue or red in color. The color in a diamond is caused by the presence
of minor elements.(Diamond, Encarta Online, 2001) Unlike graphite, diamonds are good
conductors of heat and poor electrical conductors. [In fact], diamond conducts heat better than
anything-five times better than the second best element, silver.(The Mineral Diamond,
1996) Because of its hardness, diamond is often used as an abrasive. Diamond coatings can
also be synthetically produced by heating carbon dioxide over a metal surface with a series of
lasers. These diamond coatings have the potential to greatly extend the lifetime of precision
dies, drills, and saw blades.(Encarta, 2000)

An interesting physical property of diamond is its melting point. Diamond has the
highest melting point (3820 K) [of any substance].(The Mineral Diamond, 1996) Another
fascinating property of diamond is its lattice density. The atoms of diamond are packed closer
together than are the atoms of any other substance.(The Mineral Diamond, 1996) A table
contrasting the physical characteristics of graphite and diamond follows.
Physical Characteristics
Color

Luster
Transparency
Crystal System
Crystal Habits
Hardness(Mohs)
Specific Gravity
Cleavage
Fracture
Streak
Best Field Indicator

Diamond
variable-pale yellows,
browns, grays, and also
white, blue, black, reddish,
greenish and colorless
adamantine to waxy
crystals are transparent to
translucent in rough crystals
Isometric
cubes and octahedrons
10
3.5 (above average)
perfect in 4 directions
forming octahedrons
Conchoidal
White
Extreme Hardness

Graphite
Black silver

metallic to dull
crystals are opaque
hexagonal
massive lamellar veins and
earthy masses
1-2
2.2 (well below average)
perfect in 1 direction
Flaky
Black gray to brownish gray
Softness, luster, density and
streak

(The data contained in this table was taken from the following
site: http://mineral.galleries.com/Minerals/elements/. )

A phase diagram for carbon, showing graphite and diamond follows.

P
R
E
S
S
U
R
E

Graphite

TEMPERATURE

Graphite and diamond also have different thermodynamic properties. Since graphite is
the stable form of carbon, it has a heat of formation of zero. To contrast, diamond has a heat of
formation of +1.895 kJ/mol. Other thermodynamic data is represented in the table below, which
includes carbon in the gas phase to serve as a comparison. Notice that the entropy of graphite is
larger than that of diamond; this is due again to diamonds compact crystal lattice. In other
words, it is much more ordered than the graphite structure. Carbon is found in nature in solid
form, this accounts for the largely positive enthalpy and Gibbs values. A lot of energy is needed
to vaporize carbon.

Graphite
Diamond
Gaseous Carbon

Standard Enthalpy
of
Formation(kJ/mol)
0
+1.895
+716.68

Standard Gibbs
Energy of
Formation(kJ/mol)
0
+2.900
+671.26

Standard Molar
Entropy(J/Kmol)
5.740
2.377
158.10

(The data found in this table was taken from Elements of Physical Chemistry, Peter Atkins.)

Amorphous carbon is actually made up of tiny crystal-like bits of graphite with varying
amounts of other elements, which are considered impurities.(Carbon, Encarta Online,
2001) Some examples of amorphous carbons are charcoal, soot, and a coal-derived fuel called
coke. The higher the carbon content in coal, the more energy is released in combustion. The
coal industry divides coal up into various grades depending on the amount of carbon in the coal
and the amount of impurities. The highest grade, anthracite, contains about 90% carbon. Lower
grades include bituminous coal, which is 76% to 90% carbon, subbituminous coal, with 60% to
80% carbon and lignite, with 55% to 73% carbon.(Carbon, Encarta Online, 2001) Coal was

formed from buried fossils that were exposed to high pressure and temperature over a long time
span.
In 1985 chemists created a new allotrope of carbon by heating graphite to extremely
high temperatures.(Carbon, Encarta Online, 2001) This new allotrope, C60, was given the
name buckminsterfullerene after an architect-engineer, R. Buckminster Fuller who designed
geodesic domes. A structural diagram of buckminsterfullerene is shown in Figure 1.
Because the C60 sphere is hollow, other atoms can be trapped within it. When a graphite
sheet soaked in LaCl3 solution is subjected to vaporization-condensation experiments, a
substance with formula LaC60 is formed.(Buckyballs) Experiments using other metal salts in
which laser pulses were used to shrink the ball of carbon atoms yielded such compounds as
CsC48 and KC44. Other experiments have produced new materials with C60. For example,
C60 doped with potassium is a superconductor below 18 K.(Buckyballs) Three-dimensional
polymers and tubes of carbon called nanotubes have also been made using this new allotrope of
carbon. As for the future of C60, derivatives of buckminsterfullerene have been found
Diamond
Diamond is one of the best known allotropes of carbon, whose hardness and high dispersion of light make it useful
for industrial applications and jewelry. Diamond is the hardest known natural mineral, which makes it an excellent
abrasive and makes it hold polish and luster extremely well. No known naturally occurring substance can scratch, let
alone cut, a diamond.
The market for industrial-grade diamonds operates much differently from its gem-grade counterpart. Industrial
diamonds are valued mostly for their hardness and heat conductivity, making many of
the gemological characteristics of diamond, including clarity and color, mostly irrelevant. This helps explain why
80% of mined diamonds (equal to about 100 million carats or 20,000 kg annually), unsuitable for use as gemstones
and known as bort, are destined for industrial use. In addition to mined diamonds, synthetic diamonds found
industrial applications almost immediately after their invention in the 1950s; another 400 million carats (80,000 kg)
of synthetic diamonds are produced annually for industrial usenearly four times the mass of natural diamonds
mined over the same period.
The dominant industrial use of diamond is in cutting, drilling (drill bits), grinding (diamond edged cutters), and
polishing. Most uses of diamonds in these technologies do not require large diamonds; in fact, most diamonds that
are gem-quality can find an industrial use. Diamonds are embedded in drill tips or saw blades, or ground into a
powder for use in grinding and polishing applications. Specialized applications include use in laboratories as
containment for high pressure experiments (see diamond anvil), high-performance bearings, and limited use in
specialized windows.
With the continuing advances being made in the production of synthetic diamond, future applications are beginning
to become feasible. Garnering much excitement is the possible use of diamond as a semiconductor suitable to
build microchipsfrom, or the use of diamond as a heat sink in electronics. Significant research efforts
in Japan, Europe, and the United States are under way to capitalize on the potential offered by diamond's unique
material properties, combined with increased quality and quantity of supply starting to become available from
synthetic diamond manufacturers.

Each carbon atom in a diamond is covalently bonded to four other carbons in a tetrahedron. These tetrahedrons
together form a 3-dimensional network of puckered six-membered rings of atoms. This stable network of covalent
bonds and the three dimensional arrangement of bonds is the reason that diamond is so strong.

Graphite
Graphite (named by Abraham Gottlob Werner in 1789, from the Greek : "to draw/write", for its use in
pencils) is one of the most common allotropes of carbon. Unlike diamond, graphite is an electrical conductor, and
can be used, for instance, as the material in the electrodes of an electrical arc lamp. Graphite holds the distinction of
being the most stable form of carbon under standard conditions. Therefore, it is used in thermochemistry as
the standard state for defining the heat of formation of carbon compounds.
Graphite is able to conduct electricity, due to delocalization of the pi bond electrons above and below the planes of
the carbon atoms. These electrons are free to move, so are able to conduct electricity. However, the electricity is only
conducted along the plane of the layers. In diamond all four outer electrons of each carbon atom are 'localised'
between the atoms in covalent bonding. The movement of electrons is restricted and diamond does not conduct an
electric current. In graphite, each carbon atom uses only 3 of its 4 outer energy level electrons in covalently bonding
to three other carbon atoms in a plane. Each carbon atom contributes one electron to a delocalised system of
electrons that is also a part of the chemical bonding. The delocalised electrons are free to move throughout the plane.
For this reason, graphite conducts electricity along the planes of carbon atoms, but does not conduct in a direction at
right angles to the plane.
Graphite powder is used as a dry lubricant. Although it might be thought that this industrially important property is
due entirely to the loose interlamellar coupling between sheets in the structure, in fact in a vacuum environment
(such as in technologies for use in space), graphite was found to be a very poor lubricant. This fact led to the
discovery that graphite's lubricity is due to adsorbed air and water between the layers, unlike other layered dry
lubricants such as molybdenum disulfide. Recent studies suggest that an effect called superlubricity can also account
for this effect.
When a large number of crystallographic defects bind these planes together, graphite loses its lubrication properties
and becomes what is known as pyrolytic carbon, a useful material in blood-contacting implants such
as prosthetic heart valves.
Natural and crystalline graphites are not often used in pure form as structural materials due to their shear-planes,
brittleness and inconsistent mechanical properties.
In its pure glassy (isotropic) synthetic forms, pyrolytic graphite and carbon fiber graphite is an extremely strong,
heat-resistant (to 3000 C) material, used in reentry shields for missile nosecones, solid rocket engines, high
temperature reactors, brake shoes and electric motor brushes.
Intumescent or expandable graphites are used in fire seals, fitted around the perimeter of a fire door. During a fire
the graphite intumesces (expands and chars) to resist fire penetration and prevent the spread of fumes. A typical start
expansion temperature (SET) is between 150 and 300 degrees Celsius.
Density: its specific gravity is 2.3 which makes it lighter than diamond.
Effect of heat: it is the most stable allotrope of carbon. At a temperature of 2500 degree Celsius, it can be
transformed into diamond. At about 700 degree Celsius it burns in pure oxygen forming carbon dioxide.

Chemical activity: it is slightly more reactive than diamond. This is because the reactants are able to penetrate
between the hexagonal layers of carbon atoms in graphite. It is unaffected by ordinary solvents, dilute acids, or fused
alkalis. However, chromic acid oxidises it to carbon dioxide.

Amorphous carbon
Amorphous carbon is the name used for carbon that does not have any crystalline structure. As with
all glassy materials, some short-range order can be observed, but there is no long-range pattern of atomic positions.
While entirely amorphous carbon can be made, natural amorphous carbon (such as soot) actually contains
microscopic crystals of graphite, [1] sometimes diamond [2]. On the macroscopic scale, amorphous carbon has no
definite structure as it conisists of small irregular cystals, but on the nanomicroscopic scale, we can see it is made of
regularly arranged carbon atoms.
Coal and soot are both informally called amorphous carbon. However, both are products of pyrolysis (the process of
decomposing a substance by the action of heat), which does not produce true amorphous carbon under normal
conditions. The coal industry divides coal up into various grades depending on the amount of carbon present in the
sample compared to the amount of impurities. The highest grade, anthracite, is about 90 percent carbon and 10%
other elements. Bituminous coalis about 75-90 percent carbon, and lignite is the name for coal that is around 55
percent carbon.

Buckminsterfullerenes
Part of a series of articles on
Nanomaterials
Fullerenes
Carbon nanotubes
Fullerene chemistry
Applications
In popular culture
Timeline
Carbon allotropes
Nanoparticles
Quantum dots
Nanostructures
Colloidal gold
Colloidal silver
Iron nanoparticles
Platinum nanoparticles

The buckminsterfullerenes, or usually just fullerenes for short, were discovered

in 1985 by a team of scientists from Rice University and
the University of Sussex, three of whom were awarded the 1996 Nobel Prize in
Chemistry. They are named for the resemblance of their alliotropic structure to
the geodesic structures devised by the scientist and architect Richard
Buckminster "Bucky" Fuller. Fullerenes are molecules of varying sizes
composed entirely of carbon, which take the form of a hollow sphere, ellipsoid,
or tube.
As of the early twenty-first century, the chemical and physical properties of
fullerenes are still under heavy study, in both pure and applied research labs. In
April 2003, fullerenes were under study for potential medicinal use binding
specific antibiotics to the structure to target resistant bacteria and even target
certain cancer cells such as melanoma.

See also
Nanotechnology
This box: view talk edit

Buckyballs
Spherical fullerenes are also called buckyballs.

Carbon nanotubes
Carbon nanotubes, also called buckytubes, are cylindrical carbon molecules with novel properties that make them
potentially useful in a wide variety of applications (e.g., nano-electronics, optics, materials applications, etc.). They
exhibit extraordinary strength, unique electrical properties, and are efficient conductors of heat. Inorganic
nanotubes have also been synthesized. A nanotube (also known as a buckytube) is a member of
the fullerene structural family, which also includes buckyballs. Whereas buckyballs are spherical in shape, a
nanotube is cylindrical, with at least one end typically capped with a hemisphere of the buckyball structure. Their
name is derived from their size, since the diameter of a nanotube is on the order of a few nanometers (approximately
50,000 times smaller than the width of a human hair), while they can be up to several centimeters in length. There
are two main types of nanotubes: single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs).

Carbon nanobuds

Computer models of stable NanoBud structures

Carbon NanoBuds are a newly discovered allotrope of carbon in which fullerene like "buds" are covalently
attached to the outer sidewalls of the carbon nanotubes. This hybrid material has useful properties of both fullerenes
and carbon nanotubes. In particular, they have been found to be exceptionally good field emitters.

Aggregated diamond nanorods

Aggregated diamond nanorods, or ADNRs, are an allotrope of carbon believed to be the least compressible
material known to humankind, as measured by its isothermal bulk modulus; aggregated diamond nanorods have a
modulus of 491 gigapascals (GPa), while a conventional diamond has a modulus of 442 GPa. ADNRs are also 0.3%
denser than regular diamond. The ADNR material is also harder than type IIa diamond and ultrahard fullerite.

Glassy carbon
Glassy carbon is a class of non-graphitizing carbon which is widely used as an electrode material
in electrochemistry, as well as for high temperature crucibles and as a component of some prosthetic devices. It was
first produced by workers at the laboratories of The General Electric Company, UK, in the early 1960s, using
cellulose as the starting material. A short time later, Japanese workers produced a similar material from phenolic
resin.
It was first produced by Bernard Redfern in the mid 1950's at the laboratories of The Carborundum
Company, Trafford Park, Manchester, UK. He set out to develop a polymer matrix to mirror a diamond structure and
discovered a resole (phenolic) resin that would, with special preparation, set without a catalyst. Using this resin the
first glassy carbon was produced. Patents were filed some of which were withdrawn in the interests of national
security. Original research samples of resin and product exist.
The preparation of glassy carbon involves subjecting the organic precursors to a series of heat treatments at
temperatures up to 3000oC. Unlike many non-graphitizing carbons, they are impermeable to gases and are

chemically extremely inert, especially those which have been prepared at very high temperatures. It has been
demonstrated that the rates of oxidation of certain glassy carbons in oxygen, carbon dioxide or water vapour are
lower than those of any other carbon. They are also highly resistant to attack by acids. Thus, while
normal graphite is reduced to a powder by a mixture of concentrated sulfuric and nitric acids at room temperature,
glassy carbon is unaffected by such treatment, even after several months.

Carbon nanofoam
Carbon nanofoam is the fifth known allotrope of carbon discovered in 1997 by Andrei V. Rode and co-workers at
the Australian National University in Canberra. It consists of a low-density cluster-assembly of carbon atoms strung
together in a loose three-dimensional web.
Each cluster is about 6 nanometers wide and consists of about 4000 carbon atoms linked in graphite-like sheets that
are given negative curvature by the inclusion of heptagons among the regular hexagonal pattern. This is the opposite
of what happens in the case of buckminsterfullerenes, in which carbon sheets are given positive curvature by the
inclusion of pentagons.
The large-scale structure of carbon nanofoam is similar to that of an aerogel, but with 1% of the density of
previously produced carbon aerogels - only a few times the density of air at sea level. Unlike carbon aerogels,
carbon nanofoam is a poor electrical conductor.

Lonsdaleite (hexagonal diamond)

Lonsdaleite is a hexagonal allotrope of the carbon allotrope diamond, believed to form when meteoric graphite falls
to Earth. The great heat and stress of the impact transforms the graphite into diamond, but retains graphite's
hexagonal crystallattice.
Lonsdaleite was first identified from the Canyon Diablo meteorite at Barringer Crater (also known as Meteor Crater)
in Arizona. It was first discovered in 1967. Lonsdaleite occurs as microscopic crystals associated with diamond in
the Canyon Diablo meteorite; Kenna meteorite, New Mexico; and Allan Hills (ALH) 77283, Victoria
Land, Antarctica meteorite. It has also been reported from the Tunguska impact site, Russia.

Linear Acetylenic Carbon (LAC)

Chemists in the USA have recently reported (ca 1995) an allotrope of carbon consisting of long chains of carbon
atoms where the alternate carbon-carbon bonds are of different lengths; and consist of C-C bonds and CC bonds.
The same polymer was synthesized in early 1960s by group of Soviet chemists and was called carbyne
(Russian: ). It appeared to be a semiconductor that is very sensitive to light, thus it was suggested to use it
in photodiodes and similar devices.
Carbyne, or polyyne, is also another name for Linear Acetylenic Carbon [1] (LAC) the carbon allotrope that has the
chemical structure [2] -(C:::C)n- .Carbon in this modification is linear with sp orbital hybridisation, and is
a polymer with alternating single and triple bonds. This type of carbyne is of considerable interest
to nanotechnology as its Young's modulus is forty times that of diamond [3].

Variability of carbon

Diamond and graphite are two allotropes of carbon: pure forms

of the same element that differ in structure.
The system of carbon allotropes spans an astounding range of extremes,
considering that they are all merely structural formations of the same element.

Between diamond and graphite:

Diamond crystallizes in the cubic system but graphite crystallizes in the hexagonal system.
Diamond is hardest mineral known to man (10 on Mohs scale), but graphite is one of the
softest (1 - 2 on Mohs scale).
Diamond is the ultimate abrasive, but graphite is a very good lubricant.
Diamond is an excellent electrical insulator, but graphite is a conductor of electricity.
Diamond is an excellent thermal conductor, but some forms of graphite are used for thermal
insulation (i.e. heatshields and firebreaks)

Other possible forms

Chaoite is a mineral believed to have been formed in meteorite impacts. It has been
described as slightly harder than graphite with a reflection colour of grey to white. However,
the existence of carbyne phases is disputed see the entry on chaoitefor details.
Metallic carbon: Theoretical studies have shown that carbon (diamond) when brought at
enormous pressure, there are regions in the phase diagram where it's metallic.[4] It seems
that it can also become superconducting at very low temperatures (4 kelvins). [5]
Hexagonite: in theory, instead of having the 6-arom rings of graphite, one sp carbon atom
could be inserted between each of the 6 sp2 atoms.[6]
Prismane C8 is another possible metastable form.