Carbide

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Editor-In-Chief: C. Michael Gibson, M.S., M.D. [1]


Overview

Calcium carbide.

In chemistry, a carbide is a compound of carbon with a more electronegative element. Carbides are important industrially: for example, calcium carbide is a feedstock for the chemical industry and iron carbide, Fe3C (cementite), is formed in steels to improve their properties.
Many carbides can be generally classified by chemical bonding type as follows[1]:

  • salt-like ionic compounds
  • covalent compounds
  • interstitial compounds
  • "intermediate" transition metal carbides (a group of carbides that in bonding terms sit between the salt-like and interstitial carbides).

In addition to the carbides there are other groups of binary carbon compounds, i.e.[1]

Examples

Some examples are[1]:-

See Category:Carbides for a bigger list.

Types of carbides

Ionic salts

Salt like carbides are formed by the metals of[1]

Most commonly they are salts of C22− and are called acetylides, ethynides, acetylenediides or very rarely, percarbides.
Some compounds contain other anionic species:[1]

  • C4−, sometimes called methanides (or methides) because they hydrolyse to give methane gas.
  • C34− ion, sometimes called sesquicarbides, they hydrolyse to give methylacetylene.

The naming of ionic carbides is not consistent and can be quite confusing.

Acetylides

The polyatomic ion C22− contains a triple bond between the two carbon atoms. Examples are the carbides of the alkali metals e.g. Na2C2, some alkaline earths, e.g. CaC2 and lanthanoids e.g. LaC2.[1] The C-C bond distance ranges from 109.2pm in CaC2 (similar to ethyne), to 130.3 pm in LaC2 and 134pm in UC2.[1] The bonding in LaC2 has been described in terms of LaIII with the extra electron delocalised into the antibonding orbital on C22−, explaining the metallic conduction.[1]

Methanides

The monatomic ion C4− is a very strong base, and will combine with four protons to form methane. Methanides commonly react with water to form methane, however reactions with other substances are common.
C4− + 4H+ → CH4
Examples of compounds that contain C4− are Be2C and Al4C3.[1]

Sesquicarbides

The polyatomic ion C34− is found in e.g. Li4C3, Mg2C3.[1] The ion is linear and is isoelectronic with CO2.[1] The C-C distance in Mg2C3 is 133.2 pm.[2] Mg2C3 yields methylacetylene, CH3CCH, on hydrolysis which was the first indication that it may contain C34−.

Covalent carbides

Silicon and boron form covalent carbides.[1] Silicon carbide has two similar crystalline forms, which are both related to the diamond structure.[1] Boron carbide, B4C, on the other hand has an unusual structure which includes icosahedral boron units linked by carbon atoms. In this respect boron carbide is similar to the boron rich borides. Both silicon carbide, SiC, (carborundum) and boron carbide, B4C are very hard materials and refractory. Both materials are important industrally. Boron also forms other covalent carbides, e.g. B25C.

Interstitial carbides

Properties

The carbides of the group 4, 5 and 6 transition metals (with the exception of chromium) are often described as interstitial compounds.[1] These carbides are chemically quite inert, have metallic properties and are refractory. Some exhibit a range of stoichiometries, e.g. titanium carbide, TiC. Titanium carbide and tungsten carbide are important industrially and are used to coat metals in cutting tools.[3]

Structure

The longheld view is that the carbon atoms fit into octahedral interstices in a close packed metal lattice when the metal atom radius is greater than approximately 135 pm:[1]

  • When the metal atoms are cubic close packed, (ccp), then filling all of the octahedral interstices with carbon achieves 1:1 stoichiometry with the rock salt structure, (note that in rock salt, NaCl, it is the chloride anions that are cubic close packed).
  • When the metal atoms are hexagonal close packed, (hcp), as the octahedral interstices lie directly opposite each other on either side of the layer of metal atoms, filling only only one of these with carbon achieves 2:1 stoichiometry with the CdI2 structure.

The following table [1][3]shows actual structures of the metals and their carbides. (N.B. the body centred cubic structure adopted by vanadium, niobium, tantalum, chromium, molybdenum and tungsten is not a close packed lattice.) The notation "h/2" refers to the M2C type structure described above, which is only an approximate description of the actual structures. The simple view that the lattice of the pure metal "absorbs" carbon atoms can be seen to be untrue as the packing of the metal atom lattice in the carbides is different from the packing in the pure metal.

Metal Structure of pure metal Metallic
radius (pm)
MC
- metal atom packing
MC structure M2C
- metal atom packing
M2C structure Other carbides
titanium hcp 147 ccp rock salt
zirconium hcp 160 ccp rock salt
hafnium hcp 159 ccp rock salt
vanadium cubic body centered 134 ccp rock salt hcp h/2 V4C3
niobium cubic body centered 146 ccp rock salt hcp h/2 Nb4C3
tantalum cubic body centered 146 ccp rock salt hcp h/2 Ta4C3
chromium cubic body centered 128 Cr23C6, Cr3C,
Cr7C3, Cr3C2
molybdenum cubic body centered 139 hexagonal hcp h/2 Mo3C2
tungsten cubic body centered 139 hexagonal hcp h/2

For a long time the non stoichiometric phases were believed to be disordered with a random filling of the interstices, however short and longer range ordering has been detected[4].

Intermediate transition metal carbides

In these the transition metal ion is smaller than the critical 135 pm and the structures are not interstitial but are more complex. [1] Multiple stoichiometries are common, for example iron forms a number of carbides, Fe3C, Fe7C3 and Fe2C.[1] The best known is cementite, Fe3C, which is present in steels.[1] These carbides are more reactive than the interstitial carbides, for example the carbides of Cr, Mn, Fe, Co and Ni all are hydrolysed by dilute acids and sometimes by water, to give a mixture of hydrogen and hydrocarbons.[1] These compounds share features with both the inert interstitals and the more reactive salt-like carbides.[1]

References

  1. 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20
  2. Crystal Structure of Magnesium Sesquicarbide Fjellvag H. and Pavel K. Inorg. Chem. 1992, 31, 3260
  3. 3.0 3.1 Carbides: transition metal solid state chemistry Peter Ettmayer & Walter Lengauer, Encyclopedia of Inorganic Chemistry Editor in chief R. Bruce King Pub 1994 John Wiley & Sons ISBN 0-471-93620-0
  4. Order and disorder in transition metal carbides and nitrides: experimental and theoretical aspects C.H. de Novion and J.P. Landesman Pure & Appl. Chem., 57, 10,(1985)1391

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