Allotropy

Allotropy or allotropism is the property of some chemical elements to exist in two or more different forms, known as allotropes of these elements. Allotropes are different structural modifications of an element; the atoms of the element are bonded together in a different manner. For example, the allotropes of carbon include diamond (where the carbon atoms are bonded together in a tetrahedral lattice arrangement), graphite (where the carbon atoms are bonded together in sheets of a hexagonal lattice), graphene (single sheets of graphite), and fullerenes (where the carbon atoms are bonded together in spherical, tubular, or ellipsoidal formations). The term allotropy is used for elements only, not for compounds. The more general term, used for any crystalline material, is polymorphism. Allotropy refers only to different forms of an element within the same phase (i.e. different solid, liquid or gas forms); the changes of state between solid, liquid and gas in themselves are not considered allotropy.

Different allotropes of carbon are-

Diamond
Diamond is one well known allotrope of carbon. The hardness and high dispersion of light of diamond make it useful for both industrial applications and jewellery. Diamond is the hardest known natural mineral. This makes it an excellent abrasive and makes it hold polish and luster extremely well. No known naturally occurring substance can cut (or even scratch) a diamond, except another 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 tones annually) are 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 tones) 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 microchips from, 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 six-membered carbon rings (similar to cyclohexane), in the chair conformation, allowing for zero bond angle strain. This stable network of covalent bonds and hexagonal rings, is the reason that diamond is so incredibly strong

Structure

The crystal structure of a diamond is a face-centered cubic or FCC lattice. Each carbon atom joins four other carbon atoms in regular tetrahedrons (triangular prisms). Based on the cubic

form and its highly symmetrical arrangement of atoms, diamond crystals can develop into several different shapes, known as 'crystal habits'.

Physical properties of diamond

Hardness: Diamond is a perfect "10", defining the top of the hardness scale, and by absolute measures four times harder than sapphire (which is #9 on that scale). Clarity: Diamond is transparent over a larger range of wavelengths (from the ultraviolet into the far infrared) than is any other solid or liquid substance - nothing else even comes close. Thermal Conductivity: Diamond conducts heat better than anything - five times better than the second best element, Silver! Melting Point: Diamond has the highest melting point (3820 degrees Kelvin) Lattice Density: The atoms of Diamond are packed closer together than are the atoms of any other substance . Tensile Strength: Diamond has the highest tensile strength of any material, at 2.8 gigapascals. However, that does not quite translate into the strongest rope or cable, as diamond has cleavage planes which support crack propagation. The strongest ropes can likely be made from another carbon material, carbon nanotubes, as they should not suffer from the effects of cracks and break. Still, if a long, thin, perfect crystal of diamond could be manufactured, it would offer the highest possible pulling strength

Graphite
Graphite (named by Abraham Gottlob Werner in 1789, from the Greek (graphein, "to draw/write", for its use in pencils) is one of the most common allotropes of carbon. Unlike diamond, graphite is an electrical conductor. Thus, it can be used in, for instance, electrical arc lamp electrodes. Likewise, under standard conditions, graphite is the most stable form of carbon. Therefore, it is used in thermochemistry as the standard state for defining the heat of formation of carbon compounds. Graphite conducts 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. Density: graphite's specific gravity is 2.3, which makes it lighter than diamonds. Effect of heat: it is the most stable allotrope of carbon. At high temperatures and pressures (roughly 2000 C and 5 GPa), it can be transformed into diamond. At about 700 C it burns in 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.

Structure
Graphite has a layered, planar structure. In each layer, the carbon atoms are arranged in a hexagonal lattice with separation of 0.142 nm, and the distance between planes is 0.335 nm.[8] The two known forms of graphite, alpha (hexagonal) and beta (rhombohedral), have very similar physical properties (except that the graphene layers stack slightly differently).[9] The hexagonal graphite may be either flat or buckled.[10] The alpha form can be converted to the beta form through mechanical treatment and the beta form reverts to the alpha form when it is heated above 1300 C.[11] The layering contributes to its lower density.

Physical properties of graphite

Melting Point Graphite has a high melting point above 3000, like that of diamond, the other allotrope of carbon. Hence, it is stable over a wide range of temperatures. Density As there is a lot of vacant space between the graphite sheets, held by the weak covalent bonds, the density of graphite is 2.09 to 2.33 g/cc, which is lower than that of diamond. The measured specific gravity of graphite is approximately 2.26 g/cc, however, it depends upon the purity of graphite. Graphite with a higher ash content shows a specific gravity higher than 2.26, while natural graphite has a lower specific gravity or density due to the trapped porosity. Solubility Graphite is insoluble in water as well as other organic solvents. There are no attractive forces that occur between the solvent molecules and the carbons atoms in graphite and so it fails to dissolve in any of the organic solvents. Electrical Conductivity There is vast delocalization of electrons within the carbon layers of graphite. The delocalized electrons are free to move and are able to conduct electricity, thus making graphite a good conductor of electricity.

Buckminsterfullerenes
The buckminsterfullerenes, or usually just fullerenes or buckyballs 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 allotropic 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.

Structure
The structure of a buckminsterfullerene is a truncated icosahedron with 60 vertices and 32 faces (20 hexagons and 12 pentagons where no pentagons share a vertex) with a carbon atom at the vertices of each polygon and a bond along each polygon edge. The van der Waals diameter of a C60 molecule is about 1.01 nanometers (nm). The nucleus to nucleus diameter of a C60 molecule is about 0.71 nm. The C60 molecule has two bond lengths. The 6:6 ring bonds (between two hexagons) can be considered "double bonds" and are shorter than the 6:5 bonds (between a hexagon and a pentagon). Its average bond length is 0.14 nm. Each carbon atom in the structure is bonded covalently with 3 others.

Physical properties of fullerenes

Property Soft and slippery Explanation Few covalent bonds holding the

molecules together but only weak Vander Waals forces between molecules. Brittle Soft weak crystals typical of covalent substances No movement of electrons available from one molecule to the next. The exception could be the formation of Nano-tubes that are capable of conducting electricity along their length. These are the subject of some experiments in micro electronics There are only very weak Van der Waal's attractions between the carbon atoms and the water molecules whereas the carbon atoms are bonded very tightly to one another in the molecules. Typical of covalent crystals where only Van der Waal's interactions have to be broken for melting.

Electrical insulator

Insoluble in water.

Low m.p. solids

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 produced, most amorphous carbon actually contains microscopic crystals of graphite-like, or even diamond-like carbon. Coal and soot or carbon black are informally called amorphous carbon. However, they 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% carbon and 10% other elements. Bituminous coal is about 7590% carbon, and lignite is the name for coal that is around 55% carbon.it is the softest of all types.

Uses of natural graphite

Natural graphite is mostly consumed for refractories, batteries, steelmaking, expanded graphite, brake linings, foundry facings and lubricants. Graphene, which occurs naturally in graphite, has unique physical properties and might be one of the strongest substances known; however, the process of separating it from graphite will require some technological development before it is economically feasible to use it in industrial processes.

Refractories
This end-use begins before 1900 with the graphite crucible used to hold molten metal; this is now a minor part of refractories. In the mid-1980s, the carbon-magnesite brick became important, and a bit later the alumina-graphite shape. Currently the order of importance is alumina-graphite shapes, carbon-magnesite brick, monolithics (gunning and ramming mixes), and then crucibles.Crucibles began using very large flake graphite, and carbon-magnesite brick requiring not quite so large flake graphite; for these and others there is now much more flexibility in size of flake required, and amorphous graphite is no longer restricted to low-end refractories.

Batteries
The use of graphite in batteries has been an increasing in the last 30 years. Natural and synthetic graphite are used to construct the anode of all major battery technologies. The Li-ion battery utilizes more graphite than lithium carbonate.The demand for batteries, primarily nickel-metalhydride and Li-ion batteries has caused a growth in graphite demand in the late 1980s and early 1990s.

Steelmaking
Natural graphite in this end use mostly goes into carbon rising in molten steel, although it can be used to lubricate the dies used to extrude hot steel.

Brake linings
Natural amorphous and fine flake graphite are used in brake linings or brake shoes for heavier (nonautomotive) vehicles, and became important with the need to substitute for asbestos.

Foundry facings and lubricants

A foundry facing mild wash is a water-based paint of amorphous or fine flake graphite. Painting the inside of a mold with it and letting it dry leaves a fine graphite coat that will ease separation of the object cast after the hot metal has cooled. Graphite lubricants are specialty items for use at

very high or very low temperatures, as forging die lubricant, an antiseize agent, a gear lubricant for mining machinery, and to lubricate locks.

Potential applications of graphene

Integrated circuits
Graphene has the ideal properties to be an excellent component of integrated circuits. Graphene has a high carrier mobility, as well as low noise, allowing it to be used as the channel in a fieldeffect transistor. The issue is that single sheets of graphene are hard to produce, and even harder to make on top of an appropriate substrate.

Electro chromic devices

Graphene oxide can be reversibly reduced and oxidized using electrical stimulus. Controlled reduction and oxidation in two-terminal devices containing multilayer graphene oxide films are shown to result in switching between partially reduced graphene oxide and graphene, a process which modifies the electronic and optical properties.

Room temperature distillation of ethanol for fuel and human consumption

Graphene oxide membranes will allow water vapour to pass through, but have been shown to be impermeable to all other liquids and gases including helium. This phenomenon has been used for further distilling of vodka to higher alcohol concentrations, in a room-temperature laboratory, without the application of heat or vacuum normally used in traditional distillation methods.

Desalination
Research suggests that graphene filters could outperform other techniques of desalination by a significant margin.

Solar cells
The USC Viterbi School of Engineering lab reported the large scale production of highly transparent graphene films by chemical vapour deposition in 2008. In this process, researchers create ultra-thin graphene sheets by first depositing carbon atoms in the form of graphene films on a nickel plate from methane gas.

Use in research of fullerenes

While past cancer research has involved radiation therapy, Photodynamic therapy is important to study because breakthroughs in treatments for tumour cells will give more options to patients with different conditions. More recent experiments using HeLa cells in cancer research involves the development of new photosensitizers with increased ability to be absorbed by cancer cells and still trigger cell death. It is also important that a new photosensitizer does not stay in the body for a long time to prevent unwanted cell damage. Fullerenes can be made to be absorbed by HeLa cells. The C60 derivatives can be delivered to the cells by using the functional groups Lphenylalanine, folic acid, and L-arginine among others .The purpose for functionalizing the fullerenes is to increase the solubility of the molecule by the cancer cells. Cancer cells take up these molecules at an increased rate because of an up regulation of transporters in the cancer cell; in this case amino acid transporters will bring in the L-arginine and L-phenylalanine functional groups of the fullerenes.