carbide
carbide, any of a class of chemical compounds in which carbon is combined with a metallic or semimetallic element. Calcium carbide is important chiefly as a source of acetylene and other chemicals, whereas the carbides of silicon, tungsten, and several other elements are valued for their physical hardness, strength, and resistance to chemical attack even at very high temperatures. Iron carbide (cementite) is an important constituent of steel and cast iron.
Preparation of carbides
Carbides are prepared from carbon and an element of similar or lower electronegativity, usually either a metal or a metal oxide, at temperatures of 1,000–2,800 °C (1,800–5,100 °F). Almost any carbide can be prepared by one of several general methods. The first method involves direct combination of the elements at high temperatures (2,000 °C [3,600 °F] or higher). The second method is the reaction of a compound of a metal, usually an oxide, with carbon at high temperature. Two additional methods involve reaction of a metal or metal salt with a hydrocarbon, usually acetylene, C2H2. In one of the methods, the heated metal reacts with a gaseous hydrocarbon; in the other, a metal is dissolved in liquid ammonia, NH3, and the hydrocarbon is bubbled through the solution. Carbides that are prepared with acetylene are called acetylides and contain the C22− anion. For example, the alkali metal acetylides are best prepared by dissolving the alkali metal in liquid ammonia and passing acetylene through the solution. These compounds, which have the general formula M2C2 (where M is the metal), are colourless, crystalline solids. They react violently with water and, when heated in air, are oxidized to the carbonate. The alkaline-earth carbides also are acetylides. They have the general formula MC2 and are prepared by heating the alkaline-earth metal with acetylene above 500 °C (900 °F).
Classification of carbides
Classification of carbides based on structural type is rather difficult, but three broad classifications arise from general trends in their properties. The most electropositive metals form ionic or saltlike carbides, the transition metals in the middle of the periodic table tend to form what are called interstitial carbides, and the nonmetals of electronegativity similar to that of carbon form covalent or molecular carbides.
Ionic carbides
Ionic carbides have discrete carbon anions of the forms C4−, sometimes called methanides since they can be viewed as being derived from methane, (CH4); C22−, called acetylides and derived from acetylene (C2H2); and C34−, derived from allene (C3H4). The best-characterized methanides are probably beryllium carbide (Be2C) and aluminum carbide (Al4C3). Beryllium oxide (BeO) and carbon react at 2,000 °C (3,600 °F) to produce the brick-red beryllium carbide, whereas pale yellow aluminum carbide is prepared from aluminum and carbon in a furnace. Aluminum carbide reacts as a typical methanide with water to produce methane. Al4C3 + 12H2O → 4Al(OH)3 + 3CH4
There are many acetylides that are well known and well characterized. In addition to those of the alkali metals and the alkaline-earth metals mentioned above, lanthanum (La) forms two different acetylides, and copper (Cu), silver (Ag), and gold (Au) form explosive acetylides. Zinc (Zn), cadmium (Cd), and mercury (Hg) also form acetylides, although they are not as well characterized. The most important of these compounds is calcium carbide, CaC2. The primary use for calcium carbide is as a source of acetylene for use in the chemical industry. Calcium carbide is synthesized industrially from calcium oxide (lime), CaO, and carbon in the form of coke at about 2,200 °C (4,000 °F). Pure calcium carbide has a high melting point (2,300 °C [4,200 °F]) and is a colourless solid. The reaction of CaC2 with water yields C2H2 and a significant amount of heat, so the reaction is carried out under carefully controlled conditions.
CaO + 3C → CaC2 + CO
CaC2 + 2H2O → C2H2 + Ca(OH)2
Calcium carbide also reacts with nitrogen gas at elevated temperatures (1,000–1,200 °C [1,800–2,200 °F]) to form calcium cyanamide, CaCN2.
CaC2 + N2 → CaCN2 + C
This is an important industrial reaction because CaCN2 finds extensive use as a fertilizer owing to its reaction with water to produce cyanamide, H2NCN. Most MC2 acetylides have the CaC2 structure, which is derived from the cubic sodium chloride (NaCl) structure. The C2 units lie parallel along the cell axes, causing a distortion of the cell from cubic to tetragonal.
Interstitial carbides
Interstitial carbides are derived primarily from relatively large transition metals that act as a host lattice for the small carbon atoms, which occupy the interstices of the close-packed metal atoms. (See crystal for a discussion of packing arrangements in solids.) Interstitial carbides are characterized by extreme hardness but at the same time extreme brittleness. They have very high melting points (typically about 3,000–4,000 °C [5,400–7,200 °F]) and retain many of the properties associated with the metal itself, such as high conductivity of heat and electricity as well as metallic lustre. At elevated temperatures some interstitial carbides retain the mechanical properties of metals, such as malleability. Many of the early transition metals have radii that are large enough to form interstitial monocarbides, MC. The critical (i.e., minimum) radius appears to be approximately 1.35 angstroms (1.35 × 10−8 cm, or 5.32 × 10−9 inch). However, most transition metals form interstitial carbides of several stoichiometries. For example, manganese (Mn) is known to form at least five different interstitial carbides. In contrast to the ionic carbides, most interstitial carbides do not react with water and are chemically inert. Several have industrial importance, including tungsten carbide (WC) and tantalum carbide (TaC), which are used as high-speed cutting tools because of their extreme hardness and chemical inertness. Iron carbide (cementite), Fe3C, is an important component in steel.
Covalent carbides
There are only two carbides that are considered completely covalent; they are formed with the two elements that are most similar to carbon in size and electronegativity, boron (B) and silicon (Si). Silicon carbide (SiC) is known as carborundum and is prepared by the reduction of silicon dioxide (SiO2) with elemental carbon in an electric furnace. This material, like diamond, is extremely hard and is used industrially as an abrasive. It is chemically inert and has a diamond structure in which each silicon atom and each carbon atom are surrounded tetrahedrally by four atoms of the other type. Boron carbide (B4C) has similar properties. It is also extremely hard and inert. It is prepared by the reduction of boron oxide (B2O3) with carbon in an electric furnace. In the structure of B4C, the boron atoms occur in icosahedral groups of 12, and the carbon atoms occur in linear chains of three. Another boron carbide (BC3), which has a graphitelike structure, is produced from the reaction of benzene (C6H6) and boron trichloride (BCl3) at 800 °C (1,500 °F).
