Chemical element with atomic number 6
<Carbon (from Latin: carbo "coal") is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table.[13] Carbon makes up only about 0.025 percent of Earth's crust.[14] Three isotopes occur naturally, 12C and 13C being stable, while 14C is a radionuclide, decaying with a half-life of about 5,730 years.[15] Carbon is one of the few elements known since antiquity.[16]
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 (about 18.5%) after oxygen.[17]
The atoms of carbon can bond together in diverse ways, resulting in various allotropes of carbon. The best known allotropes are graphite, diamond, and buckminsterfullerene.[18] 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 (hence its name, from the Greek verb "γράφειν" which means "to write"), 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, more than any other element, with almost ten million compounds described to date,[19] and yet that number is but a fraction of the number of theoretically possible compounds under standard conditions. For this reason, carbon has often been referred to as the "king of the elements".[20]
Characteristics
Theoretically predicted phase diagram of carbon
The allotropes of carbon include graphite, one of the softest known substances, and diamond, the hardest naturally occurring substance. It bonds readily with other small atoms, including other carbon atoms, and is capable of forming multiple stable covalent bonds with suitable multivalent atoms. Carbon is known to form almost ten million compounds, a large majority of all chemical compounds.[19] 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 ± 300 °C; 7,820 ± 540 °F),[2][3] so it sublimes at about 3,900 K (3,630 °C; 6,560 °F).[21][22] 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, C6(CO2H)6, which preserves the hexagonal units of graphite while breaking up the larger structure.[23]
Carbon sublimes in a carbon arc, which has a temperature of about 5800 K (5,530 °C or 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, which are weaker reducing agents at room temperature.
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 (1.8–1.9), 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 (C−C), 66.7 pm (C=C) and 60.3 pm (C≡C), 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.[24]
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 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:
- Fe
3O
4 + 4 C(s) → 3 Fe(s) + 4 CO(g)
Carbon monoxide can be recycled to smelt even more iron:
- Fe
3O
4 + 4 CO(g) → 3 Fe(s) + 4 CO
2(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.
The system of carbon allotropes spans a range of extremes:
Allotropes
Atomic carbon 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,[30][31] carbon nanotubes,[32] carbon nanobuds[33] and nanofibers.[34][35] Several other exotic allotropes have also been discovered, such as lonsdaleite,[36] glassy carbon,[37] carbon nanofoam[38] and linear acetylenic carbon (carbyne).[39]
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.[40] The process of separating it from graphite will require some further technological development before it is economical for industrial processes.[41] 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.[42]
A large sample of glassy carbon
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 (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.[43] 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, 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 (ΔfG°(diamond, 298 K) = 2.9 kJ/mol[44]) under normal conditions (298 K, 105 Pa) and transform into graphite.[18] Due to a high activation energy barrier, the transition into graphite is so slow at normal temperature that it is unnoticeable. The bottom left corner of the phase diagram for carbon has not been scrutinized experimentally. However, a recent computational study employing density functional theory methods reached the conclusion that as T → 0 K and p → 0 Pa, diamond becomes more stable than graphite by approximately 1.1 kJ/mol.[45] Under some conditions, carbon crystallizes as lonsdaleite, a hexagonal crystal lattice with all atoms covalently bonded and properties similar to those of diamond.[36]
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 (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).[30] Carbon nanotubes (buckytubes) are structurally similar to buckyballs, except that each atom is bonded trigonally in a curved sheet that forms a hollow cylinder.[31][32] Nanobuds were first reported in 2007 and are hybrid buckytube/buckyball materials (buckyballs are covalently bonded to the outer wall of a nanotube) that combine the properties of both in a single structure.[33]
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.[46] Similarly, glassy carbon contains a high proportion of closed porosity,[37] 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[39] has the chemical structure[39] −(C:::C)n−. 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.[47]
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.[48]
In the vapor phase, some of the carbon is in the form of dicarbon (C
2). When excited, this gas glows green.
Occurrence
Graphite ore, shown with a penny for scale
Carbon is the fourth most abundant chemical element in the observable universe by mass after hydrogen, helium, and oxygen. In July 2020, astronomers reported evidence that carbon was formed mainly in white dwarf stars, particularly those bigger than two solar masses.[49][50] Carbon is abundant in the Sun, stars, comets, and in the atmospheres of most planets.[51] Some meteorites contain microscopic diamonds that were formed when the solar system was still a protoplanetary disk.[52] Microscopic diamonds may also be formed by the intense pressure and high temperature at the sites of meteorite impacts.[53]
In 2014 NASA announced a greatly upgraded database for tracking polycyclic aromatic hydrocarbons (PAHs) in the universe. More than 20% of the carbon in the universe may be associated with PAHs, complex compounds of carbon and hydrogen without oxygen.[54] These compounds figure in the PAH world hypothesis where they are hypothesized to have a role in abiogenesis and formation of life. PAHs seem to have been formed "a couple of billion years" after the Big Bang, are widespread throughout the universe, and are associated with new stars and exoplanets.[51]
It has been estimated that the solid earth as a whole contains 730 ppm of carbon, with 2000 ppm in the core and 120 ppm in the combined mantle and crust.[55] Since the mass of the earth is 5.972×1024 kg, this would imply 4360 million gigatonnes of carbon. This is much more than the amount of carbon in the oceans or atmosphere (below).
In combination with oxygen in carbon dioxide, carbon is found in the Earth's atmosphere (approximately 900 gigatonnes of carbon — each ppm corresponds to 2.13 Gt) and dissolved in all water bodies (approximately 36,000 gigatonnes of carbon). Carbon in the biosphere has been estimated at 550 gigatonnes but with a large uncertainty, due mostly to a huge uncertainty in the amount of terrestrial deep subsurface bacteria.[56] Hydrocarbons (such as coal, petroleum, and natural gas) contain carbon as well. Coal "reserves" (not "resources") amount to around 900 gigatonnes with perhaps 18,000 Gt of resources.[57] Oil reserves are around 150 gigatonnes. Proven sources of natural gas are about 175×1012 cubic metres (containing about 105 gigatonnes of carbon), but studies estimate another 900×1012 cubic metres of "unconventional" deposits such as shale gas, representing about 540 gigatonnes of carbon.[58]
Carbon is also found in 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 (about 18.5%) after oxygen.[17]
The atoms of carbon can bond together in diverse ways, resulting in various allotropes of carbon. The best known allotropes are graphite, diamond, and buckminsterfullerene.[18] 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 (hence its name, from the Greek verb "γράφειν" which means "to write"), 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, more than any other element, with almost ten million compounds described to date,[19] and yet that number is but a fraction of the number of theoretically possible compounds under standard conditions. For this reason, carbon has often been referred to as the "king of the elements".[20]
The allotropes of carbon include graphite, one of the softest known substances, and diamond, the hardest naturally occurring substance. It bonds readily with other small atoms, including other carbon atoms, and is capable of forming multiple stable covalent bonds with suitable multivalent atoms. Carbon is known to form almost ten million compounds, a large majority of all chemical compounds.[19] 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 ± 300 °C; 7,820 ± 540 °F),[2][3] so it sublimes at about 3,900 K (3,630 °C; 6,560 °F).[21][22] 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, C6(CO2H)6, which preserves the hexagonal units of graphite while breaking up the larger structure.[23]
Carbon sublimes in a carbon arc, which has a temperature of about 5800 K (5,530 °C or 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, which are weaker reducing agents at room temperature.
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 (1.8–1.9), 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 (C−C), 66.7 pm (C=C) and 60.3 pm (C≡C), 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.[24]
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 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:
- Fe
3O
4 + 4 C(s) → 3 Fe(s) + 4 CO(g)
Carbon monoxide can be recycled to smelt even more iron:
- Fe
3Otungsten