Carbon (from Latin: carbo “coal”) is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds. There are three naturally occurring isotopes, with 12C and 13C being stable, while 14C is radioactive, decaying with a half-life of about 5,730 years. Carbon is one of the few elements known since antiquity.
There are several allotropes of carbon of which the best known are graphite, diamond, and amorphous carbon. The physical properties of carbon vary widely with the allotropic form. For example, diamond is highly transparent, while graphite is opaque and black. Diamond is the hardest naturally-occurring material known, while graphite is soft enough to form a streak on paper (hence its name, from the Greek word “γράφω” which means “to write”). Diamond has a very low electrical conductivity, while graphite is a very good conductor. Under normal conditions, diamond, carbon nanotube 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. 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 other 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 more compounds than any other element, with almost ten million pure organic compounds described to date, which in turn are a tiny fraction of such compounds that are theoretically possible under standard conditions.
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. It is present in all known life forms, and in the human body carbon is the second most abundant element by mass (about 18.5%) after oxygen. This abundance, together with the unique diversity of organic compounds and their unusual polymer-forming ability at the temperatures commonly encountered on Earth, make this element the chemical basis of all known life.
The different forms or allotropes of carbon include the hardest naturally occurring substance, diamond, and also one of the softest known substances, graphite. Moreover, it has an affinity for bonding with other small atoms, including other carbon atoms, and is capable of forming multiple stable covalent bonds with such atoms. As a result, carbon is known to form almost ten million different compounds; the large majority of all chemical compounds. Carbon also has the highest sublimation point of all elements. At atmospheric pressure it has no melting point as its triple point is at 10.8 ± 0.2 MPa and 4,600 ± 300 K (~4,330 °C or 7,820 °F), so it sublimes at about 3,900 K.
Carbon sublimes in a carbon arc which has a temperature of about 5,800 K (5,530 °C; 9,980 °F). Thus, irrespective of its allotropic form, carbon remains solid at higher temperatures than the highest melting point metals such as tungsten or rhenium. Although thermodynamically prone to oxidation, carbon resists oxidation more effectively than elements such as iron and copper that are weaker reducing agents at room temperature.
Carbon compounds form the basis of all known life on Earth, and the carbon-nitrogen cycle provides some of the energy produced by the Sun and other 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 reduce such metal oxides as iron oxide to the metal. This exothermic reaction is used in the iron and steel industry to control the carbon content of steel:
Fe3O4 + 4 C(s) → 3 Fe(s) + 4 CO(g)
with sulfur to form carbon disulfide and with steam in the coal-gas reaction:
C(s) + H2O(g) → CO(g) + H2(g).
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.
As of 2009, graphene appears to be the strongest material ever tested. However, the process of separating it from graphite will require some technological development before it is economical enough to be used in industrial processes.
The system of carbon allotropes spans a range of extremes:
Atomic carbon is a very short-lived species and, therefore, carbon is stabilized in various multi-atomic structures with different 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 (carbyne)
The amorphous form is an assortment of carbon atoms in a non-crystalline, irregular, glassy state, which is essentially graphite but not held in a crystalline macrostructure. It is present as a powder, and is the main constituent of substances such as charcoal, lampblack (soot) 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 (the sheets slip easily past one another). 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.
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, thus making 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 in terms of resistance to scratching. Contrary to the popular belief that “diamonds are forever”, they are in fact thermodynamically unstable under normal conditions and transform into graphite. However, due to a high activation energy barrier, the transition into graphite is so extremely slow at room temperature as to be unnoticeable. Under some conditions, carbon crystallizes as lonsdaleite. This form has a hexagonal crystal lattice where all atoms are covalently bonded. Therefore, all properties of lonsdaleite are close to those of diamond.
Fullerenes have a graphite-like structure, but instead of purely hexagonal packing, they also contain pentagons (or even heptagons) of carbon atoms, which bend the sheet into spheres, ellipses or cylinders. The properties of fullerenes (split into buckyballs, buckytubes and nanobuds) 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 (the best-known and simplest is the soccerball-shaped C60 buckminsterfullerene).
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 bucky tube/buckyball materials (buckyballs are covalently bonded to the outer wall of a nanotube) 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/m3. 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-(C:::C)n-. Carbon in this modification is linear with sp orbital hybridization, 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 the hardest known material – diamond.
Carbon is the fourth most abundant chemical element in the universe by mass after hydrogen, helium, and oxygen. Carbon is abundant in the Sun, stars, comets, and in the atmospheres of most planets. Some meteorites contain microscopic diamonds that were formed when the solar system was still a protoplanetary disk. Microscopic diamonds may also be formed by the intense pressure and high temperature at the sites of meteorite impacts.
In combination with oxygen in carbon dioxide, carbon is found in the Earth’s atmosphere (approximately 810 gigatonnes of carbon) and dissolved in all water bodies (approximately 36,000 gigatonnes of carbon). Around 1,900 gigatonnes of carbon are present in the biosphere. Hydrocarbons (such as coal, petroleum, and natural gas) contain carbon as well—coal “reserves” (not “resources”) amount to around 900 gigatonnes, and oil reserves around 150 gigatonnes. Proven sources of natural gas are about 175 1012 cubic metres (representing about 105 gigatonnes carbon), but it is estimated that there are also about 900 1012 cubic metres of “unconventional” gas such as shale gas, representing about 540 gigatonnes of carbon. Carbon is also locked up as methane hydrates in polar regions and under the seas. Various estimates of the amount of carbon this represents have been made: 500 to 2500 Gt, or 3000 Gt. (In the past, quantities of hydrocarbons were greater. In the period from 1751 to 2008 about 347 gigatonnes of carbon were released as carbon dioxide to the atmosphere from burning of fossil fuels.)
Carbon is a major component in very large masses of carbonate rock (limestone, dolomite, marble and so on). Coal is the largest commercial source of mineral carbon, accounting for 4,000 gigatonnes or 80% of fossil carbon fuel. It is also rich in carbon – for example, anthracite contains 92–98%.
As for individual carbon allotropes, graphite is found in large quantities in the United States (mostly in New York and Texas), Russia, Mexico, Greenland, and India. Natural diamonds occur in the rock kimberlite, found in ancient volcanic “necks”, or “pipes”. Most diamond deposits are in Africa, notably in South Africa, Namibia, Botswana, the Republic of the Congo, and Sierra Leone. There are also deposits in Arkansas, Canada, the Russian Arctic, Brazil and in Northern and Western Australia. Diamonds are now also being recovered from the ocean floor off the Cape of Good Hope. However, though diamonds are found naturally, about 30% of all industrial diamonds used in the U.S. are now made synthetically.
Carbon-14 is formed in upper layers of the troposphere and the stratosphere, at altitudes of 9–15 km, by a reaction that is precipitated by cosmic rays. Thermal neutrons are produced that collide with the nuclei of nitrogen-14, forming carbon-14 and a proton.
Isotopes of carbon are atomic nuclei that contain six protons plus a number of neutrons (varying from 2 to 16). Carbon has two stable, naturally occurring isotopes. The isotope carbon-12 (12C) forms 98.93% of the carbon on Earth, while carbon-13 (13C) forms the remaining 1.07%. The concentration of 12C is further increased in biological materials because biochemical reactions discriminate against 13C. In 1961, the International Union of Pure and Applied Chemistry (IUPAC) adopted the isotope carbon-12 as the basis for atomic weights. Identification of carbon in NMR experiments is done with the isotope 13C.
Carbon-14 (14C) is a naturally occurring radioisotope which occurs in trace amounts on Earth of up to 1 part per trillion (0.0000000001%), mostly confined to the atmosphere and superficial deposits, particularly of peat and other organic materials. This isotope decays by 0.158 MeV β− emission. Because of its relatively short half-life of 5730 years, 14C is virtually absent in ancient rocks, but is created in the upper atmosphere (lower stratosphere and upper troposphere) by interaction of nitrogen with cosmic rays. The abundance of 14C in the atmosphere and in living organisms is almost constant, but decreases predictably in their bodies after death. This principle is used in radiocarbon dating, invented in 1949, which has been used extensively to determine the age of carbonaceous materials with ages up to about 40,000 years.
There are 15 known isotopes of carbon and the shortest-lived of these is 8C which decays through proton emission and alpha decay and has a half-life of 1.98739×10−21s The exotic 19C exhibits a nuclear halo, which means its radius is appreciably larger than would be expected if the nucleus were a sphere of constant density.