Carbon

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. Three isotopes occur naturally, 12C and 13C being stable, while 14C is a radionuclide, decaying with a half-life of about 5,730 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 (about 18.5%) after oxygen.

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. 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, 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”.

History

The English name carbon comes from the Latin carbo for coal and charcoal, whence also comes the French charbon, meaning charcoal. In German, Dutch and Danish, the names for carbon are Kohlenstoff, koolstof and kulstof respectively, all literally meaning coal-substance.

Carbon was discovered in prehistory and was known in the forms of soot and charcoal to the earliest human civilizations. Diamonds were known probably as early as 2500 BCE in China, while carbon in the form of charcoal was made around Roman times by the same chemistry as it is today, by heating wood in a pyramid covered with clay to exclude air.

In 1722, René Antoine Ferchault de Réaumur demonstrated that iron was transformed into steel through the absorption of some substance, now known to be carbon. In 1772, Antoine Lavoisier showed that diamonds are a form of carbon; when he burned samples of charcoal and diamond and found that neither produced any water and that both released the same amount of carbon dioxide per gram. In 1779, Carl Wilhelm Scheele showed that graphite, which had been thought of as a form of lead, was instead identical with charcoal but with a small admixture of iron, and that it gave “aerial acid” (his name for carbon dioxide) when oxidized with nitric acid. In 1786, the French scientists Claude Louis Berthollet, Gaspard Monge and C. A. Vandermonde confirmed that graphite was mostly carbon by oxidizing it in oxygen in much the same way Lavoisier had done with diamond. Some iron again was left, which the French scientists thought was necessary to the graphite structure. In their publication they proposed the name carbone (Latin carbonum) for the element in graphite which was given off as a gas upon burning graphite. Antoine Lavoisier then listed carbon as an element in his 1789 textbook.

A new allotrope of carbon, fullerene, that was discovered in 1985 includes nanostructured forms such as buckyballs and nanotubes. Their discoverers – Robert Curl, Harold Kroto and Richard Smalley – received the Nobel Prize in Chemistry in 1996. The resulting renewed interest in new forms lead to the discovery of further exotic allotropes, including glassy carbon, and the realization that “amorphous carbon” is not strictly amorphous.

Natural occurence

Carbon is the fourth most abundant chemical element in the observable 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 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. 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.

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. 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. 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. 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.

Carbon is also found in methane hydrates in polar regions and under the seas. Various estimates put this carbon between 500, 2500 Gt, or 3,000 Gt.

In the past, quantities of hydrocarbons were greater. According to one source, 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. Another source puts the amount added to the atmosphere for the period since 1750 at 879 Gt, and the total going to the atmosphere, sea, and land (such as peat bogs) at almost 2,000 Gt.

Carbon is a constituent (about 12% by mass) of the very large masses of carbonate rock (limestone, dolomite, marble and so on). Coal is very rich in carbon (anthracite contains 92–98%) and is the largest commercial source of mineral carbon, accounting for 4,000 gigatonnes or 80% of fossil fuel.

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. Diamond deposits have also been found 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. Diamonds are found naturally, but about 30% of all industrial diamonds used in the U.S. are now manufactured.

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. As such, 1.5%×10−10 of atmospheric carbon dioxide contains carbon-14.

Carbon-rich asteroids are relatively preponderant in the outer parts of the asteroid belt in our solar system. These asteroids have not yet been directly sampled by scientists. The asteroids can be used in hypothetical space-based carbon mining, which may be possible in the future, but is currently technologically impossible.

Production

Graphite

Commercially viable natural deposits of graphite occur in many parts of the world, but the most important sources economically are in China, India, Brazil and North Korea. Graphite deposits are of metamorphic origin, found in association with quartz, mica and feldspars in schists, gneisses and metamorphosed sandstones and limestone as lenses or veins, sometimes of a metre or more in thickness. Deposits of graphite in Borrowdale, Cumberland, England were at first of sufficient size and purity that, until the 19th century, pencils were made simply by sawing blocks of natural graphite into strips before encasing the strips in wood. Today, smaller deposits of graphite are obtained by crushing the parent rock and floating the lighter graphite out on water.

There are three types of natural graphite—amorphous, flake or crystalline flake, and vein or lump. Amorphous graphite is the lowest quality and most abundant. Contrary to science, in industry “amorphous” refers to very small crystal size rather than complete lack of crystal structure. Amorphous is used for lower value graphite products and is the lowest priced graphite. Large amorphous graphite deposits are found in China, Europe, Mexico and the United States. Flake graphite is less common and of higher quality than amorphous; it occurs as separate plates that crystallized in metamorphic rock. Flake graphite can be four times the price of amorphous. Good quality flakes can be processed into expandable graphite for many uses, such as flame retardants. The foremost deposits are found in Austria, Brazil, Canada, China, Germany and Madagascar. Vein or lump graphite is the rarest, most valuable, and highest quality type of natural graphite. It occurs in veins along intrusive contacts in solid lumps, and it is only commercially mined in Sri Lanka.

According to the USGS, world production of natural graphite was 1.1 million tonnes in 2010, to which China contributed 800,000 t, India 130,000 t, Brazil 76,000 t, North Korea 30,000 t and Canada 25,000 t. No natural graphite was reported mined in the United States, but 118,000 t of synthetic graphite with an estimated value of $998 million was produced in 2009.

Diamond

The diamond supply chain is controlled by a limited number of powerful businesses, and is also highly concentrated in a small number of locations around the world (see figure).

Only a very small fraction of the diamond ore consists of actual diamonds. The ore is crushed, during which care has to be taken in order to prevent larger diamonds from being destroyed in this process and subsequently the particles are sorted by density. Today, diamonds are located in the diamond-rich density fraction with the help of X-ray fluorescence, after which the final sorting steps are done by hand. Before the use of X-rays became commonplace, the separation was done with grease belts; diamonds have a stronger tendency to stick to grease than the other minerals in the ore.

Historically diamonds were known to be found only in alluvial deposits in southern India. India led the world in diamond production from the time of their discovery in approximately the 9th century BC to the mid-18th century AD, but the commercial potential of these sources had been exhausted by the late 18th century and at that time India was eclipsed by Brazil where the first non-Indian diamonds were found in 1725.

Diamond production of primary deposits (kimberlites and lamproites) only started in the 1870s after the discovery of the diamond fields in South Africa. Production has increased over time and now an accumulated total of 4.5 billion carats have been mined since that date. About 20% of that amount has been mined in the last 5 years alone, and during the last ten years 9 new mines have started production while 4 more are waiting to be opened soon. Most of these mines are located in Canada, Zimbabwe, Angola, and one in Russia.

In the United States, diamonds have been found in Arkansas, Colorado and Montana. In 2004, a startling discovery of a microscopic diamond in the United States led to the January 2008 bulk-sampling of kimberlite pipes in a remote part of Montana.

Today, most commercially viable diamond deposits are in Russia, Botswana, Australia and the Democratic Republic of Congo. In 2005, Russia produced almost one-fifth of the global diamond output, reports the British Geological Survey. Australia has the richest diamantiferous pipe with production reaching peak levels of 42 metric tons (41 long tons; 46 short tons) per year in the 1990s. There are also commercial deposits being actively mined in the Northwest Territories of Canada, Siberia (mostly in Yakutia territory; for example, Mir pipe and Udachnaya pipe), Brazil, and in Northern and Western Australia.

Economic use

Carbon is essential to all known living systems, and without it life as we know it could not exist (see alternative biochemistry). The major economic use of carbon other than food and wood is in the form of hydrocarbons, most notably the fossil fuel methane gas and crude oil (petroleum). Crude oil is distilled in refineries by the petrochemical industry to produce gasoline, kerosene, and other products. Cellulose is a natural, carbon-containing polymer produced by plants in the form of wood, cotton, linen, and hemp. Cellulose is used primarily for maintaining structure in plants. Commercially valuable carbon polymers of animal origin include wool, cashmere and silk. Plastics are made from synthetic carbon polymers, often with oxygen and nitrogen atoms included at regular intervals in the main polymer chain. The raw materials for many of these synthetic substances come from crude oil.

The uses of carbon and its compounds are extremely varied. It can form alloys with iron, of which the most common is carbon steel. Graphite is combined with clays to form the ‘lead’ used in pencils used for writing and drawing. It is also used as a lubricant and a pigment, as a molding material in glass manufacture, in electrodes for dry batteries and in electroplating and electroforming, in brushes for electric motors and as a neutron moderator in nuclear reactors.

Charcoal is used as a drawing material in artwork, barbecue grilling, iron smelting, and in many other applications. Wood, coal and oil are used as fuel for production of energy and heating. Gem quality diamond is used in jewelry, and industrial diamonds are used in drilling, cutting and polishing tools for machining metals and stone. Plastics are made from fossil hydrocarbons, and carbon fiber, made by pyrolysis of synthetic polyester fibers is used to reinforce plastics to form advanced, lightweight composite materials.

Carbon fiber is made by pyrolysis of extruded and stretched filaments of polyacrylonitrile (PAN) and other organic substances. The crystallographic structure and mechanical properties of the fiber depend on the type of starting material, and on the subsequent processing. Carbon fibers made from PAN have structure resembling narrow filaments of graphite, but thermal processing may re-order the structure into a continuous rolled sheet. The result is fibers with higher specific tensile strength than steel.

Carbon black is used as the black pigment in printing ink, artist’s oil paint and water colours, carbon paper, automotive finishes, India ink and laser printer toner. Carbon black is also used as a filler in rubber products such as tyres and in plastic compounds. Activated charcoal is used as an absorbent and adsorbent in filter material in applications as diverse as gas masks, water purification, and kitchen extractor hoods, and in medicine to absorb toxins, poisons, or gases from the digestive system. Carbon is used in chemical reduction at high temperatures. Coke is used to reduce iron ore into iron (smelting). Case hardening of steel is achieved by heating finished steel components in carbon powder. Carbides of silicon, tungsten, boron and titanium, are among the hardest known materials, and are used as abrasives in cutting and grinding tools. Carbon compounds make up most of the materials used in clothing, such as natural and synthetic textiles and leather, and almost all of the interior surfaces in the built environment other than glass, stone and metal.

Diamonds

The diamond industry falls into two categories: one dealing with gem-grade diamonds and the other, with industrial-grade diamonds. While a large trade in both types of diamonds exists, the two markets function dramatically differently.

Unlike precious metals such as gold or platinum, gem diamonds do not trade as a commodity: there is a substantial mark-up in the sale of diamonds, and there is not a very active market for resale of diamonds.

Industrial diamonds are valued mostly for their hardness and heat conductivity, with the gemological qualities of clarity and color being mostly irrelevant. About 80% of mined diamonds (equal to about 100 million carats or 20 tonnes annually) are unsuitable for use as gemstones are relegated for industrial use (known as bort). synthetic diamonds, invented in the 1950s, found almost immediate industrial applications; 3 billion carats (600 tonnes) of synthetic diamond is produced annually.

The dominant industrial use of diamond is in cutting, drilling, grinding, and polishing. Most of these applications do not require large diamonds; in fact, most diamonds of gem-quality except for their small size can be used industrially. 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 cell), high-performance bearings, and limited use in specialized windows. With the continuing advances in the production of synthetic diamonds, new applications are becoming feasible. Garnering much excitement is the possible use of diamond as a semiconductor suitable for microchips, and because of its exceptional heat conductance property, as a heat sink in electronics.

Biology

Carbon occurs in all known organic life and is the basis of organic chemistry. When united with hydrogen, it forms various hydrocarbons that are important to industry as refrigerants, lubricants, solvents, as chemical feedstock for the manufacture of plastics and petrochemicals, and as fossil fuels.

When combined with oxygen and hydrogen, carbon can form many groups of important biological compounds including sugars, lignans, chitins, alcohols, fats, and aromatic esters, carotenoids and terpenes. With nitrogen it forms alkaloids, and with the addition of sulfur also it forms antibiotics, amino acids, and rubber products. With the addition of phosphorus to these other elements, it forms DNA and RNA, the chemical-code carriers of life, and adenosine triphosphate (ATP), the most important energy-transfer molecule in all living cells.

Safety

Pure carbon has extremely low toxicity to humans and can be handled safely in the form of graphite or charcoal. It is resistant to dissolution or chemical attack, even in the acidic contents of the digestive tract. Consequently, once it enters into the body’s tissues it is likely to remain there indefinitely. Carbon black was probably one of the first pigments to be used for tattooing, and Ötzi the Iceman was found to have carbon tattoos that survived during his life and for 5200 years after his death. Inhalation of coal dust or soot (carbon black) in large quantities can be dangerous, irritating lung tissues and causing the congestive lung disease, coalworker’s pneumoconiosis. Diamond dust used as an abrasive can be harmful if ingested or inhaled. Microparticles of carbon are produced in diesel engine exhaust fumes, and may accumulate in the lungs. In these examples, the harm may result from contaminants (e.g., organic chemicals, heavy metals) rather than from the carbon itself.

Carbon generally has low toxicity to life on Earth; but carbon nanoparticles are deadly to Drosophila.

Carbon may burn vigorously and brightly in the presence of air at high temperatures. Large accumulations of coal, which have remained inert for hundreds of millions of years in the absence of oxygen, may spontaneously combust when exposed to air in coal mine waste tips, ship cargo holds and coal bunkers, and storage dumps.

In nuclear applications where graphite is used as a neutron moderator, accumulation of Wigner energy followed by a sudden, spontaneous release may occur. Annealing to at least 250 °C can release the energy safely, although in the Windscale fire the procedure went wrong, causing other reactor materials to combust.

The great variety of carbon compounds include such lethal poisons as tetrodotoxin, the lectin ricin from seeds of the castor oil plant Ricinus communis, cyanide (CN−), and carbon monoxide; and such essentials to life as glucose and protein.