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Carbide

January 22, 2023

For the software development tool targeting the Symbian OS, see Carbide.c++. For the metallic compound commonly used in machine tools, see Tungsten carbide. For the town in West Virginia, see Carbide, Wetzel County, West Virginia.

In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece.[1]

Lattice structure of titanium carbide

Interstitial / Metallic carbides

The carbides of the group 4, 5 and 6 transition metals (with the exception of chromium) are often described as interstitial compounds.[2] These carbides have metallic properties and are refractory. Some exhibit a range of stoichiometries, being a non-stoichiometric mixture of various carbides arising due to crystal defects. Some of them, including titanium carbide and tungsten carbide, are important industrially and are used to coat metals in cutting tools.[3]

The long-held 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:[2]

  • 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.[4]
  • 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 one of these with carbon achieves 2:1 stoichiometry with the CdI2 structure.[4]

The following table[2][3] shows structures of the metals and their carbides. (N.B. the body centered 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, although it is technically correct that the carbon atoms fit into the octahedral interstices of a close-packed metal lattice.

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 bcc 134 ccp rock salt hcp h/2 V4C3
niobium bcc 146 ccp rock salt hcp h/2 Nb4C3
tantalum bcc 146 ccp rock salt hcp h/2 Ta4C3
chromium bcc 128 Cr23C6, Cr3C,
Cr7C3, Cr3C2
molybdenum bcc 139 hexagonal hcp h/2 Mo3C2
tungsten bcc 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.[5]

Iron forms a number of carbides, Fe3C, Fe7C3 and Fe2C. The best known is cementite, Fe3C, which is present in steels. These carbides are more reactive than the interstitial carbides; for example, the carbides of Cr, Mn, Fe, Co and Ni are all hydrolysed by dilute acids and sometimes by water, to give a mixture of hydrogen and hydrocarbons. These compounds share features with both the inert interstitials and the more reactive salt-like carbides.[2]

Some metals, such as lead and tin, are believed not to form carbides under any circumstances.[6] There exists however a mixed titanium-tin carbide, which is a two-dimensional conductor.[7]

Chemical classification of carbides

Carbides can be generally classified by the chemical bonds type as follows:

  1. salt-like (ionic),
  2. covalent compounds,
  3. interstitial compounds, and
  4. "intermediate" transition metal carbides.

Examples include calcium carbide (CaC2), silicon carbide (SiC), tungsten carbide (WC; often called, simply, carbide when referring to machine tooling), and cementite (Fe3C),[2] each used in key industrial applications. The naming of ionic carbides is not systematic.

Salt-like / saline / ionic carbides

Salt-like carbides are composed of highly electropositive elements such as the alkali metals, alkaline earth metals, lanthanides, actinides, and group 3 metals (scandium, yttrium, and lutetium). Aluminium from group 13 forms carbides, but gallium, indium, and thallium do not. These materials feature isolated carbon centers, often described as "C4−", in the methanides or methides; two-atom units, "C2−2", in the acetylides; and three-atom units, "C4−3", in the allylides.[2] The graphite intercalation compound KC8, prepared from vapour of potassium and graphite, and the alkali metal derivatives of C60 are not usually classified as carbides.[8]

Methanides

Methanides are a subset of carbides distinguished by their tendency to decompose in water producing methane. Three examples are aluminium carbide Al4C3, magnesium carbide Mg2C[9] and beryllium carbide Be2C.

Transition metal carbides are not saline: their reaction with water is very slow and is usually neglected. For example, depending on surface porosity, 5–30 atomic layers of titanium carbide are hydrolyzed, forming methane within 5 minutes at ambient conditions, following by saturation of the reaction.[10]

Note that methanide in this context is a trivial historical name. According to the IUPAC systematic naming conventions, a compound such as NaCH3 would be termed a "methanide", although this compound is often called methylsodium.[11]

Acetylides/ethynides

Several carbides are assumed to be salts of the acetylide anion C2−2 (also called percarbide, by analogy with peroxide), which has a triple bond between the two carbon atoms. Alkali metals, alkaline earth metals, and lanthanoid metals form acetylides, for example, sodium carbide Na2C2, calcium carbide CaC2, and LaC2.[2] Lanthanides also form carbides (sesquicarbides, see below) with formula M2C3. Metals from group 11 also tend to form acetylides, such as copper(I) acetylide and silver acetylide. Carbides of the actinide elements, which have stoichiometry MC2 and M2C3, are also described as salt-like derivatives of C2−2.

The C–C triple bond length ranges from 119.2 pm in CaC2 (similar to ethyne), to 130.3 pm in LaC2 and 134 pm in UC2. The bonding in LaC2 has been described in terms of LaIII with the extra electron delocalised into the antibonding orbital on C2−2, explaining the metallic conduction.[2]

Allylides

The polyatomic ion C4−3, sometimes called allylide, is found in Li4C3 and Mg2C3. The ion is linear and is isoelectronic with CO2.[2] The C–C distance in Mg2C3 is 133.2 pm.[12] Mg2C3 yields methylacetylene, CH3CCH, and propadiene, CH2CCH2, on hydrolysis, which was the first indication that it contains C4−3.

Covalent carbides

The carbides of silicon and boron are described as "covalent carbides", although virtually all compounds of carbon exhibit some covalent character. Silicon carbide has two similar crystalline forms, which are both related to the diamond structure.[2] 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 (also known as carborundum) and boron carbide are very hard materials and refractory. Both materials are important industrially. Boron also forms other covalent carbides, such as B25C.

Molecular carbides

 
The complex [Au6C(PPh3)6]2+, containing a carbon-gold core

Metal complexes containing C are known as metal carbido complexes. Most common are carbon-centered octahedral clusters, such as [Au6C(PPh3)6]2+ (where "Ph" represents a phenyl group) and [Fe6C(CO)6]2−. Similar species are known for the metal carbonyls and the early metal halides. A few terminal carbides have been isolated, such as [CRuCl2{P(C6H11)3}2].

Metallocarbohedrynes (or "met-cars") are stable clusters with the general formula M8C12 where M is a transition metal (Ti, Zr, V, etc.).

Related materials

In addition to the carbides, other groups of related carbon compounds exist:[2]

See also

References

  1. ^ Kunst, Helmut; Haase, Brigitte; Malloy, James C.; Wittel, Klaus; Nestler, Montia C.; Nicoll, Andrew R.; Erning, Ulrich; Rauscher, Gerhard (2006). "Metals, Surface Treatment". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a16_403.pub2.
  2. ^ a b c d e f g h i j k Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. pp. 318–22. ISBN 978-0-08-022057-4.
  3. ^ a b Peter Ettmayer; Walter Lengauer (1994). "Carbides: transition metal solid state chemistry". In R. Bruce King (ed.). Encyclopedia of Inorganic Chemistry. John Wiley & Sons. ISBN 978-0-471-93620-6.
  4. ^ a b Zhu, Qinqing; Xiao, Guorui; Cui, Yanwei; Yang, Wuzhang; Wu, Siqi; Cao, Guang-Han; Ren, Zhi (2021-10-15). "Anisotropic lattice expansion and enhancement of superconductivity induced by interstitial carbon doping in Rhenium". Journal of Alloys and Compounds. 878: 160290. doi:10.1016/j.jallcom.2021.160290. ISSN 0925-8388.
  5. ^ C.H. de Novion; J.P. Landesman (1985). "Order and disorder in transition metal carbides and nitrides: experimental and theoretical aspects". Pure Appl. Chem. 57 (10): 1391. doi:10.1351/pac198557101391. S2CID 59467042.
  6. ^ John Percy (1870). The Metallurgy of Lead, including Desiverization and Cupellation. London: J. Murray. p. 67. Retrieved 2013-04-06.
  7. ^ Y. C. Zhou; H. Y. Dong; B. H. Yu (2000). "Development of two-dimensional titanium tin carbide (Ti2SnC) plates based on the electronic structure investigation". Materials Research Innovations. 4 (1): 36–41. Bibcode:2000MatRI...4...36Z. doi:10.1007/s100190000065. S2CID 135756713.
  8. ^ Shriver and Atkins — Inorganic Chemistry
  9. ^ O.O. Kurakevych; T.A. Strobel; D.Y. Kim; G.D. Cody (2013). "Synthesis of Mg2C: A Magnesium Methanide". Angewandte Chemie International Edition. 52 (34): 8930–8933. doi:10.1002/anie.201303463. PMID 23824698.
  10. ^ A. I. Avgustinik; G. V. Drozdetskaya; S. S. Ordan'yan (1967). "Reaction of titanium carbide with water". Powder Metallurgy and Metal Ceramics. 6 (6): 470–473. doi:10.1007/BF00780135. S2CID 134209836.
  11. ^ Weiss, Erwin; Corbelin, Siegfried; Cockcroft, Jeremy Karl; Fitch, Andrew Nicholas (1990). "Über Metallalkyl- und -aryl-Verbindungen, 44 Darstellung und Struktur von Methylnatrium. Strukturbestimmung an NaCD3-Pulvern bei 1.5 und 300 K durch Neutronen- und Synchrotronstrahlenbeugung". Chemische Berichte. 123 (8): 1629–1634. doi:10.1002/cber.19901230807. ISSN 0009-2940.
  12. ^ Fjellvag H.; Pavel K. (1992). "Crystal Structure of Magnesium Sesquicarbide". Inorg. Chem. 31 (15): 3260. doi:10.1021/ic00041a018.

January 22, 2023
carbide, software, development, tool, targeting, symbian, metallic, compound, commonly, used, machine, tools, tungsten, carbide, town, west, virginia, wetzel, county, west, virginia, chemistry, carbide, usually, describes, compound, composed, carbon, metal, me. For the software development tool targeting the Symbian OS see Carbide c For the metallic compound commonly used in machine tools see Tungsten carbide For the town in West Virginia see Carbide Wetzel County West Virginia In chemistry a carbide usually describes a compound composed of carbon and a metal In metallurgy carbiding or carburizing is the process for producing carbide coatings on a metal piece 1 Lattice structure of titanium carbide Contents 1 Interstitial Metallic carbides 2 Chemical classification of carbides 2 1 Salt like saline ionic carbides 2 1 1 Methanides 2 1 2 Acetylides ethynides 2 1 3 Allylides 2 2 Covalent carbides 2 3 Molecular carbides 3 Related materials 4 See also 5 ReferencesInterstitial Metallic carbides Edit Tungsten carbide end mills The carbides of the group 4 5 and 6 transition metals with the exception of chromium are often described as interstitial compounds 2 These carbides have metallic properties and are refractory Some exhibit a range of stoichiometries being a non stoichiometric mixture of various carbides arising due to crystal defects Some of them including titanium carbide and tungsten carbide are important industrially and are used to coat metals in cutting tools 3 The long held 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 2 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 4 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 one of these with carbon achieves 2 1 stoichiometry with the CdI2 structure 4 The following table 2 3 shows structures of the metals and their carbides N B the body centered 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 although it is technically correct that the carbon atoms fit into the octahedral interstices of a close packed metal lattice Metal Structure of pure metal Metallic radius pm MC metal atom packing MC structure M2C metal atom packing M2C structure Other carbidestitanium hcp 147 ccp rock saltzirconium hcp 160 ccp rock salthafnium hcp 159 ccp rock saltvanadium bcc 134 ccp rock salt hcp h 2 V4C3niobium bcc 146 ccp rock salt hcp h 2 Nb4C3tantalum bcc 146 ccp rock salt hcp h 2 Ta4C3chromium bcc 128 Cr23C6 Cr3C Cr7C3 Cr3C2molybdenum bcc 139 hexagonal hcp h 2 Mo3C2tungsten bcc 139 hexagonal hcp h 2For 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 5 Iron forms a number of carbides Fe3C Fe7C3 and Fe2C The best known is cementite Fe3C which is present in steels These carbides are more reactive than the interstitial carbides for example the carbides of Cr Mn Fe Co and Ni are all hydrolysed by dilute acids and sometimes by water to give a mixture of hydrogen and hydrocarbons These compounds share features with both the inert interstitials and the more reactive salt like carbides 2 Some metals such as lead and tin are believed not to form carbides under any circumstances 6 There exists however a mixed titanium tin carbide which is a two dimensional conductor 7 Chemical classification of carbides EditCarbides can be generally classified by the chemical bonds type as follows salt like ionic covalent compounds interstitial compounds and intermediate transition metal carbides Examples include calcium carbide CaC2 silicon carbide SiC tungsten carbide WC often called simply carbide when referring to machine tooling and cementite Fe3C 2 each used in key industrial applications The naming of ionic carbides is not systematic Salt like saline ionic carbides Edit Salt like carbides are composed of highly electropositive elements such as the alkali metals alkaline earth metals lanthanides actinides and group 3 metals scandium yttrium and lutetium Aluminium from group 13 forms carbides but gallium indium and thallium do not These materials feature isolated carbon centers often described as C4 in the methanides or methides two atom units C2 2 in the acetylides and three atom units C4 3 in the allylides 2 The graphite intercalation compound KC8 prepared from vapour of potassium and graphite and the alkali metal derivatives of C60 are not usually classified as carbides 8 Methanides Edit Methanides are a subset of carbides distinguished by their tendency to decompose in water producing methane Three examples are aluminium carbide Al4C3 magnesium carbide Mg2C 9 and beryllium carbide Be2C Transition metal carbides are not saline their reaction with water is very slow and is usually neglected For example depending on surface porosity 5 30 atomic layers of titanium carbide are hydrolyzed forming methane within 5 minutes at ambient conditions following by saturation of the reaction 10 Note that methanide in this context is a trivial historical name According to the IUPAC systematic naming conventions a compound such as NaCH3 would be termed a methanide although this compound is often called methylsodium 11 Acetylides ethynides Edit Calcium carbide Several carbides are assumed to be salts of the acetylide anion C2 2 also called percarbide by analogy with peroxide which has a triple bond between the two carbon atoms Alkali metals alkaline earth metals and lanthanoid metals form acetylides for example sodium carbide Na2C2 calcium carbide CaC2 and LaC2 2 Lanthanides also form carbides sesquicarbides see below with formula M2C3 Metals from group 11 also tend to form acetylides such as copper I acetylide and silver acetylide Carbides of the actinide elements which have stoichiometry MC2 and M2C3 are also described as salt like derivatives of C2 2 The C C triple bond length ranges from 119 2 pm in CaC2 similar to ethyne to 130 3 pm in LaC2 and 134 pm in UC2 The bonding in LaC2 has been described in terms of LaIII with the extra electron delocalised into the antibonding orbital on C2 2 explaining the metallic conduction 2 Allylides Edit The polyatomic ion C4 3 sometimes called allylide is found in Li4C3 and Mg2C3 The ion is linear and is isoelectronic with CO2 2 The C C distance in Mg2C3 is 133 2 pm 12 Mg2C3 yields methylacetylene CH3CCH and propadiene CH2CCH2 on hydrolysis which was the first indication that it contains C4 3 Covalent carbides Edit The carbides of silicon and boron are described as covalent carbides although virtually all compounds of carbon exhibit some covalent character Silicon carbide has two similar crystalline forms which are both related to the diamond structure 2 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 also known as carborundum and boron carbide are very hard materials and refractory Both materials are important industrially Boron also forms other covalent carbides such as B25C Molecular carbides Edit The complex Au6C PPh3 6 2 containing a carbon gold core Metal complexes containing C are known as metal carbido complexes Most common are carbon centered octahedral clusters such as Au6C PPh3 6 2 where Ph represents a phenyl group and Fe6C CO 6 2 Similar species are known for the metal carbonyls and the early metal halides A few terminal carbides have been isolated such as CRuCl2 P C6H11 3 2 Metallocarbohedrynes or met cars are stable clusters with the general formula M8C12 where M is a transition metal Ti Zr V etc Related materials EditIn addition to the carbides other groups of related carbon compounds exist 2 graphite intercalation compounds alkali metal fullerides endohedral fullerenes where the metal atom is encapsulated within a fullerene molecule metallacarbohedrenes met cars which are cluster compounds containing C2 units tunable nanoporous carbon where gas chlorination of metallic carbides removes metal molecules to form a highly porous near pure carbon material capable of high density energy storage transition metal carbene complexes two dimensional transition metal carbides MXenesSee also EditKappa carbidesReferences Edit Kunst Helmut Haase Brigitte Malloy James C Wittel Klaus Nestler Montia C Nicoll Andrew R Erning Ulrich Rauscher Gerhard 2006 Metals Surface Treatment Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a16 403 pub2 a b c d e f g h i j k Greenwood Norman N Earnshaw Alan 1984 Chemistry of the Elements Oxford Pergamon Press pp 318 22 ISBN 978 0 08 022057 4 a b Peter Ettmayer Walter Lengauer 1994 Carbides transition metal solid state chemistry In R Bruce King ed Encyclopedia of Inorganic Chemistry John Wiley amp Sons ISBN 978 0 471 93620 6 a b Zhu Qinqing Xiao Guorui Cui Yanwei Yang Wuzhang Wu Siqi Cao Guang Han Ren Zhi 2021 10 15 Anisotropic lattice expansion and enhancement of superconductivity induced by interstitial carbon doping in Rhenium Journal of Alloys and Compounds 878 160290 doi 10 1016 j jallcom 2021 160290 ISSN 0925 8388 C H de Novion J P Landesman 1985 Order and disorder in transition metal carbides and nitrides experimental and theoretical aspects Pure Appl Chem 57 10 1391 doi 10 1351 pac198557101391 S2CID 59467042 John Percy 1870 The Metallurgy of Lead including Desiverization and Cupellation London J Murray p 67 Retrieved 2013 04 06 Y C Zhou H Y Dong B H Yu 2000 Development of two dimensional titanium tin carbide Ti2SnC plates based on the electronic structure investigation Materials Research Innovations 4 1 36 41 Bibcode 2000MatRI 4 36Z doi 10 1007 s100190000065 S2CID 135756713 Shriver and Atkins Inorganic Chemistry O O Kurakevych T A Strobel D Y Kim G D Cody 2013 Synthesis of Mg2C A Magnesium Methanide Angewandte Chemie International Edition 52 34 8930 8933 doi 10 1002 anie 201303463 PMID 23824698 A I Avgustinik G V Drozdetskaya S S Ordan yan 1967 Reaction of titanium carbide with water Powder Metallurgy and Metal Ceramics 6 6 470 473 doi 10 1007 BF00780135 S2CID 134209836 Weiss Erwin Corbelin Siegfried Cockcroft Jeremy Karl Fitch Andrew Nicholas 1990 Uber Metallalkyl und aryl Verbindungen 44 Darstellung und Struktur von Methylnatrium Strukturbestimmung an NaCD3 Pulvern bei 1 5 und 300 K durch Neutronen und Synchrotronstrahlenbeugung Chemische Berichte 123 8 1629 1634 doi 10 1002 cber 19901230807 ISSN 0009 2940 Fjellvag H Pavel K 1992 Crystal Structure of Magnesium Sesquicarbide Inorg Chem 31 15 3260 doi 10 1021 ic00041a018 Retrieved from https en wikipedia org w index php title Carbide amp oldid 1127691459, wikipedia, wiki, book, books, library,

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