Chemistry:Lithium carbide
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| Names | |
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| Preferred IUPAC name
Lithium acetylide | |
| Systematic IUPAC name
Lithium ethynediide | |
| Other names
Dilithium acetylide
Lithium dicarbon | |
| Identifiers | |
3D model (JSmol)
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| Properties | |
| Li2C2 | |
| Molar mass | 37.9034 g/mol |
| Density | 1.3 g/cm3[1] |
| Melting point | 452°C[2] |
| Reacts | |
| Solubility | insoluble in organic solvents |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
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| Infobox references | |
Lithium carbide, Li2C2, often known as dilithium acetylide, is a chemical compound of lithium and carbon, an acetylide. It is an intermediate compound produced during radiocarbon dating procedures. Li2C2 is one of an extensive range of lithium-carbon compounds which include the lithium-rich Li4C, Li6C2, Li8C3, Li6C3, Li4C3, Li4C5, and the graphite intercalation compounds LiC6, LiC12, and LiC18.
Li2C2 is the most thermodynamically-stable lithium-rich carbide[3] and the only one that can be obtained directly from the elements. It was first produced by Moissan, in 1896[4] who reacted coal with lithium carbonate.
- [math]\ce{ Li2CO3 + 4C->Li2C2 + 3CO }[/math]
The other lithium-rich compounds are produced by reacting lithium vapor with chlorinated hydrocarbons, e.g. CCl4. Lithium carbide is sometimes confused with the drug lithium carbonate, Li2CO3, because of the similarity of its name.
Preparation and chemistry
In the laboratory samples may be prepared by treating acetylene with a solution of lithium in ammonia, on −40°C, with creation of addition compound of Li2C2 • C2H2 • 2NH3 that decomposes in stream of hydrogen at room temperature giving white powder of Li2C2.
- [math]\ce{ C2H2 + 2Li -> Li2C2 + H2 }[/math]
Samples prepared in this manner generally are poorly crystalline. Crystalline samples may be prepared by a reaction between molten lithium and graphite at over 1000 °C.[3] Li2C2 can also be prepared by reacting CO2 with molten lithium.
- [math]\ce{ 10Li + 2CO2 -> Li2C2 + 4Li2O }[/math]
Other method for production of Li2C2 is heating of metallic lithium in atmosphere of ethylene.
- [math]\ce{ 6Li + C2H4 -> Li2C2 + 4LiH }[/math]
Lithium carbide hydrolyzes readily to form acetylene:
- [math]\ce{ Li2C2 + 2H2O -> 2LiOH + C2H2 }[/math]
Lithium hydride reacts with graphite at 400°C forming lithium carbide.
- [math]\ce{ 2LiH + 4C -> Li2C2 + C2H2 }[/math]
Also Li2C2 can be formed when organometallic compound n-Butyllithium reacts with ethyne in THF or Et2O used as a solvent, reaction is rapid and highly exothermic.
- [math]\ce{ {C2H2} + 2BuLi ->[\ce{Et2O\ or\ THF}] {Li2C2} + 2C4H10 }[/math]
Lithium carbide reacts with acetylene in liquid ammonia rapidly to give a clear solution of lithium acetylide.
LiC≡CLi + HC≡CH → 2 LiC≡CH
Preparation of the reagent in this way sometimes improves the yield in an ethynylation over that obtained with reagent prepared from lithium and acetylene.
Structure
Li2C2 is a Zintl phase compound and exists as a salt, 2Li+C22−. Its reactivity, combined with the difficulty in growing suitable single crystals, has made the determination of its crystal structure difficult. It adopts a distorted anti-fluorite crystal structure, similar to that of rubidium peroxide (Rb2O2) and caesium peroxide (Cs2O2). Each Li atom is surrounded by six carbon atoms from 4 different acetylides, with two acetylides co-ordinating side -on and the other two end-on.[3][5] The observed C-C distance of 120 pm indicates the presence of a C≡C triple bond. At high temperatures Li2C2 transforms reversibly to a cubic anti-fluorite structure.[6]
Use in radiocarbon dating
There are a number of procedures employed, some that burn the sample producing CO2 that is then reacted with lithium, and others where the carbon containing sample is reacted directly with lithium metal.[7] The outcome is the same: Li2C2 is produced, which can then be used to create species easy to use in mass spectroscopy, like acetylene and benzene.[8] Note that lithium nitride may be formed and this produces ammonia when hydrolyzed, which contaminates the acetylene gas.
References
- ↑ R. Juza; V. Wehle; H.-U. Schuster (1967). "Zur Kenntnis des Lithiumacetylids". Zeitschrift für anorganische und allgemeine Chemie 352 (5–6): 252. doi:10.1002/zaac.19673520506.
- ↑ Savchenko, A.P.; Kshnyakina, S.A.; H.-Majorova, A.F. (1997). "Thermal properties of lithium carbide and lithium intercalation compounds of graphite". Neorganicheskie Materialy 33 (11): 1305–1307.
- ↑ 3.0 3.1 3.2 Ruschewitz, Uwe (September 2003). "Binary and ternary carbides of alkali and alkaline-earth metals". Coordination Chemistry Reviews 244 (1–2): 115–136. doi:10.1016/S0010-8545(03)00102-4.
- ↑ H. Moissan Comptes Rendus hebd. Seances Acad. Sci. 122, 362 (1896)
- ↑ Juza, Robert; Opp, Karl (November 1951). "Metallamide und Metallnitride, 24. Mitteilung. Die Kristallstruktur des Lithiumamides" (in German). Zeitschrift für anorganische und allgemeine Chemie 266 (6): 313–324. doi:10.1002/zaac.19512660606.
- ↑ U. Ruschewitz; R. Pöttgen (1999). "Structural Phase Transition in Li2C2". Zeitschrift für anorganische und allgemeine Chemie 625 (10): 1599–1603. doi:10.1002/(SICI)1521-3749(199910)625:10<1599::AID-ZAAC1599>3.0.CO;2-J.
- ↑ Swart E.R. (1964). "The direct conversion of wood charcoal to lithium carbide in the production of acetylene for radiocarbon dating". Cellular and Molecular Life Sciences 20: 47–48. doi:10.1007/BF02146038.
- ↑ University of Zurich Radiocarbon Laboratory webpage
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