Carbon
Carbon is a chemical element; it has symbol C and atomic number 6. It is nonmetallic and tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 electrons. It belongs to group 14 of the periodic table. Carbon makes up about 0.025 percent of Earth's crust. Three isotopes occur naturally, C and C being stable, while C is a radionuclide, decaying with a half-life of 5,700 years. Carbon is one of the few elements known since antiquity.
Carbon is the 15th most abundant element in the Earth's crust, and the fourth most abundant element in the universe by mass after hydrogen, helium, and oxygen. Carbon's abundance, its unique diversity of organic compounds, and its unusual ability to form polymers at the temperatures commonly encountered on Earth, enables this element to serve as a common element of all known life. It is the second most abundant element in the human body by mass after oxygen.
The atoms of carbon can bond together in diverse ways, resulting in various allotropes of carbon. Well-known allotropes include graphite, diamond, amorphous carbon, and fullerenes. The physical properties of carbon vary widely with the allotropic form. For example, graphite is opaque and black, while diamond is highly transparent. Graphite is soft enough to form a streak on paper, while diamond is the hardest naturally occurring material known. Graphite is a good electrical conductor while diamond has a low electrical conductivity. Under normal conditions, diamond, carbon nanotubes, and graphene have the highest thermal conductivities of all known materials. All carbon allotropes are solids under normal conditions, with graphite being the most thermodynamically stable form at standard temperature and pressure. They are chemically resistant and require high temperature to react even with oxygen.
The most common oxidation state of carbon in inorganic compounds is +4, while +2 is found in carbon monoxide and transition metal carbonyl complexes. The largest sources of inorganic carbon are limestones, dolomites and carbon dioxide, but significant quantities occur in organic deposits of coal, peat, oil, and methane clathrates. Carbon forms a vast number of compounds, with about two hundred million having been described and indexed; and yet that number is still only a fraction of the number of theoretically possible compounds under standard conditions.
Characteristics
Carbon in its solid state exists in several allotropes, including graphite, a soft, black, and slippery material, and diamond, the hardest naturally occurring substance. This variation in physical properties arises from differences in atomic arrangement: graphite consists of layers of hexagonally arranged carbon atoms, while diamond features a rigid three-dimensional lattice.Chemically, carbon is notable for its ability to form stable chemical bonds with many elements, particularly with other carbon atoms, and is capable of forming multiple stable covalent bonds with suitable multivalent atoms. Carbon is a component element in the large majority of all chemical compounds, with about two hundred million examples having been described in the published chemical literature. Carbon also has the highest sublimation point of all elements. At atmospheric pressure it has no melting point, as its triple point is at and, so it sublimes at about.
Compared to its well-known solid allotropes, the liquid and gaseous phases of carbon are far less studied. In the vapor phase, some of the carbon is in the form of highly reactive diatomic carbon. When excited, this gas glows green. The liquid phase of carbon is a dark, mobile, and reflective liquid that can only exist above and under pressures exceeding 100 atmospheres.
Carbon is the sixth element, with a ground-state electron configuration of 1s22s22p2, of which the four outer electrons are valence electrons. Its first four ionisation energies, 1086.5, 2352.6, 4620.5 and 6222.7 kJ/mol, are much higher than those of the heavier group-14 elements. The electronegativity of carbon is 2.5, significantly higher than the heavier group-14 elements, but close to most of the nearby nonmetals, as well as some of the second- and third-row transition metals. Carbon's covalent radii are normally taken as 77.2 pm, 66.7 pm and 60.3 pm, although these may vary depending on coordination number and what the carbon is bonded to. In general, covalent radius decreases with lower coordination number and higher bond order.
Chemical
Graphite is much more reactive than diamond at standard conditions, despite being more thermodynamically stable, as its delocalised pi system is much more vulnerable to attack. For example, graphite can be oxidised by hot concentrated nitric acid at standard conditions to mellitic acid, C66, which preserves the hexagonal units of graphite while breaking up the larger structure.Carbon-based compounds form the basis of all known life on Earth, and the carbon-nitrogen-oxygen cycle provides a small portion of the energy produced by the Sun, and most of the energy in larger stars. Although it forms an extraordinary variety of compounds, most forms of carbon are comparatively unreactive under normal conditions. At standard temperature and pressure, it resists all but the strongest oxidizers. It does not react with sulfuric acid, hydrochloric acid, chlorine or any alkalis. At elevated temperatures, carbon reacts with oxygen to form carbon oxides and will rob oxygen from metal oxides to leave the elemental metal. This exothermic reaction is used in the iron and steel industry to smelt iron and to control the carbon content of steel:
Carbon reacts with sulfur to form carbon disulfide, and it reacts with steam in the coal-gas reaction used in coal gasification:
Carbon combines with some metals at high temperatures to form metallic carbides, such as the iron carbide cementite in steel and tungsten carbide, widely used as an abrasive and for making hard tips for cutting tools.
Allotropes
is a very short-lived species and, therefore, carbon is stabilized in various multi-atomic structures with diverse molecular configurations called allotropes. The three relatively well-known allotropes of carbon are amorphous carbon, graphite, and diamond. Once considered exotic, fullerenes are nowadays commonly synthesized and used in research; they include buckyballs, carbon nanotubes, carbon nanobuds and nanofibers. Several other exotic allotropes have also been discovered, such as lonsdaleite, glassy carbon, carbon nanofoam and linear acetylenic carbon.The system of carbon allotropes spans a range of extremes:
| Graphite is one of the softest materials known. | Synthetic nanocrystalline diamond is the hardest material known. |
| Graphite is a very good lubricant, displaying superlubricity. | Diamond is the ultimate abrasive. |
| Graphite is a conductor of electricity. | Diamond is an excellent electrical insulator, and has the highest breakdown electric field of any known material. |
| Some forms of graphite are used for thermal insulation, but some other forms are good thermal conductors. | Diamond is the best known naturally occurring thermal conductor. |
| Graphite is opaque. | Diamond is highly transparent. |
| Graphite crystallizes in the hexagonal system. | Diamond crystallizes in the cubic system. |
| Amorphous carbon is completely isotropic. | Carbon nanotubes are among the most anisotropic materials known. |
Graphene is a two-dimensional sheet of carbon with the atoms arranged in a hexagonal lattice. As of 2009, graphene appears to be the strongest material ever tested. The process of separating it from graphite will require some further technological development before it is economical for industrial processes. If successful, graphene could be used in the construction of a space elevator. It could also be used to safely store hydrogen for use in a hydrogen based engine in cars.
The amorphous form is an assortment of carbon atoms in a non-crystalline, irregular, glassy state, not held in a crystalline macrostructure. It is present as a powder, and is the main constituent of substances such as charcoal, lampblack, and activated carbon. At normal pressures, carbon takes the form of graphite, in which each atom is bonded trigonally to three others in a plane composed of fused hexagonal rings, just like those in aromatic hydrocarbons. The resulting network is 2-dimensional, and the resulting flat sheets are stacked and loosely bonded through weak van der Waals forces. This gives graphite its softness and its cleaving properties. Because of the delocalization of one of the outer electrons of each atom to form a π-cloud, graphite conducts electricity, but only in the plane of each covalently bonded sheet. This results in a lower bulk electrical conductivity for carbon than for most metals. The delocalization also accounts for the energetic stability of graphite over diamond at room temperature.
File:Eight Allotropes of Carbon.svg|thumb|upright=1.35|Some allotropes of carbon: a) diamond; b) graphite; c) lonsdaleite; d–f) fullerenes amorphous carbon; h) carbon nanotube
At very high pressures, carbon forms the more compact allotrope, diamond, having nearly twice the density of graphite. Here, each atom is bonded tetrahedrally to four others, forming a 3-dimensional network of puckered six-membered rings of atoms. Diamond has the same cubic structure as silicon and germanium, and because of the strength of the carbon-carbon bonds, it is the hardest naturally occurring substance measured by resistance to scratching. Contrary to the popular belief that "diamonds are forever", they are thermodynamically unstable under normal conditions and should theoretically transform into graphite. But due to a high activation energy barrier, the transition into graphite is so slow at normal temperature that it is unnoticeable. However, at very high temperatures diamond will turn into graphite, and diamonds can burn up in a house fire. The bottom left corner of the phase diagram for carbon has not been scrutinized experimentally. Although a computational study employing density functional theory methods reached the conclusion that as and, diamond becomes more stable than graphite by approximately 1.1 kJ/mol, more recent and definitive experimental and computational studies show that graphite is more stable than diamond for, without applied pressure, by 2.7 kJ/mol at T = 0 K and 3.2 kJ/mol at T = 298.15 K. Under some conditions, carbon crystallizes as lonsdaleite, a hexagonal crystal lattice with all atoms covalently bonded and properties similar to those of diamond.
Fullerenes are a synthetic crystalline formation with a graphite-like structure, but in place of flat hexagonal cells only, some of the cells of which fullerenes are formed may be pentagons, nonplanar hexagons, or even heptagons of carbon atoms. The sheets are thus warped into spheres, ellipses, or cylinders. The properties of fullerenes have not yet been fully analyzed and represent an intense area of research in nanomaterials. The names fullerene and buckyball are given after Richard Buckminster Fuller, popularizer of geodesic domes, which resemble the structure of fullerenes. The buckyballs are fairly large molecules formed completely of carbon bonded trigonally, forming spheroids. Carbon nanotubes are structurally similar to buckyballs, except that each atom is bonded trigonally in a curved sheet that forms a hollow cylinder. Nanobuds were first reported in 2007 and are hybrid buckytube/buckyball materials that combine the properties of both in a single structure.
Of the other discovered allotropes, carbon nanofoam is a ferromagnetic allotrope discovered in 1997. It consists of a low-density cluster-assembly of carbon atoms strung together in a loose three-dimensional web, in which the atoms are bonded trigonally in six- and seven-membered rings. It is among the lightest known solids, with a density of about 2 kg/m. Similarly, glassy carbon contains a high proportion of closed porosity, but contrary to normal graphite, the graphitic layers are not stacked like pages in a book, but have a more random arrangement. Linear acetylenic carbon has the chemical structure −− . Carbon in this modification is linear with sp orbital hybridization, and is a polymer with alternating single and triple bonds. This carbyne is of considerable interest to nanotechnology as its Young's modulus is 40 times that of the hardest known material – diamond.
In 2015, a team at the North Carolina State University announced the development of another allotrope they have dubbed Q-carbon, created by a high-energy low-duration laser pulse on amorphous carbon dust. Q-carbon is reported to exhibit ferromagnetism, fluorescence, and a hardness superior to diamonds.