Triethylaluminium
| |
| Names | |
|---|---|
| IUPAC name
Triethylalumane
| |
| Identifiers | |
3D model (JSmol)
|
|
| Abbreviations | TEA |
| ChemSpider | |
| ECHA InfoCard | 100.002.382 |
| EC Number |
|
PubChem CID
|
|
CompTox Dashboard (EPA)
|
|
| |
| |
| Properties | |
| C12H30Al2 | |
| Molar mass | 228.335 g·mol−1 |
| Appearance | colorless liquid |
| Density | 0.8324 g/mL at 25 °C |
| Melting point | −46 °C (−51 °F; 227 K) |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
|
pyrophoric |
| Flash point | −18 °C |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
Triethylaluminium (TEA) is an organoaluminium compound. This volatile, colorless liquid is highly pyrophoric, igniting immediately upon exposure to air. It is normally stored in stainless steel containers either as a pure liquid or as a solution in hydrocarbon solvents such as hexane, heptane, or toluene. TEA is mainly used as a co-catalyst in the industrial production of polyethylene and for the production of medium chain alcohols.
Structure and bonding
Although called triethylaluminium, the compound has a dimeric structure with the formula Al2Et6, where Et is ethyl, CH2CH3. One pair of ethyl groups are bridging and four are terminal ligands. The two bridging carbon centres are five-coordinate. The bonding is reminiscent of that of diborane, involving 3-centred, 2-electron bonds. As in trimethylaluminium, triethylaluminium is structurally fluctional resulting rapid interchange of the terminal and bridging ethyl groups. At higher temperatures, the dimer cracks into monomeric AlEt3.[1]
Synthesis and reactions
TEA can be formed via several routes. The discovery of an efficient route was significant technologically. The multistep process can be summarized in the following reaction:[2]
- 2 Al + 3 H2 + 6 C2H4 → Al2Et6
Because of this efficient synthesis, triethylaluminium is one of the most available organoaluminium compounds.
TEA can also be generated from ethylaluminium sesquichloride (Al2Cl3Et3), which arises by treating aluminium powder with chloroethane. Reduction of ethylaluminium sesquichloride with an alkali metal such as sodium gives TEA:[3]
- 3 Al2Cl3Et3 + 9 Na → 2 Al2Et6 + 2 Al + 9 NaCl
Reactivity
The Al-C bond is polarized such that triethylaluminium is easily protonated, releasing ethane:[4]
- Al2Et6 + 6 HX → 2 Al2X6 + 6 EtH
For this reaction, even weak acids can be employed such as terminal acetylenes and alcohols.
The linkage between the pair of aluminium centres is relatively weak and can be cleaved by bases (L) to give adducts with the formula AlEt3L:
- Al2Et6 + 2 L → 2 LAlEt3
Applications
TEA is used industrially as an intermediate in the production of fatty alcohols, which are converted to detergents. The first step involves the oligomerization of ethylene, which gives a mixture of "trialkylaluminium" compounds (simplified here as octyl groups):[2]
- Al2(C2H5)6 + 18 C2H4 → Al2(C8H17)6
Subsequently, these tralkyl compounds are oxidized to aluminium alkoxides, which are then hydrolysed:
- Al2(C8H17)6 + 3/2 O2 → Al2(OC8H17)6
- Al2(OC8H17)6 + 3/2 H2O → 6 C8H17OH + 2 "Al(OH)3"
Reagent in organic and organometallic chemistry
TEA has niches uses as a precursor to other organoaluminium compounds, such as diethylaluminium cyanide:[5]
- 0.5 Al2Et6 + HCN → 1/n [Et2AlCN]n + C2H6
Pyrophoric agent
TEA ignites on contact with air and will ignite and/or decompose on contact with water, and with any other oxidizers.[6] TEA is one of the few substances volatile enough to ignite on contact with cryogenic liquid oxygen. Its easy ignition makes it particularly desirable as a rocket engine ignitor. It also can be used as a rocket fuel, but has not been for any production vehicle.[7] The SpaceX Falcon 9 heavy-lift rocket uses a triethylaluminium-triethylborane mixture as a first-stage ignitor.[8]
Triethylaluminium thickened with polyisobutylene is used as an incendiary weapon, as a pyrophoric alternative to napalm, e.g. in the M74 rockets for the M202A1 launchers.[9] In this application it is known as TPA, for thickened pyrotechnic agent or thickened pyrophoric agent. The usual amount of the thickener is 6%. The amount of thickener can be decreased to 1% if other diluents are added. For example, n-hexane, can be used with increased safety by rendering the compound non-pyrophoric until the diluent evaporates, at which point a combined fireball results from both the TEA and the hexane vapors.[10]
See also
- Triethylborane, used as an ignitor in the Pratt & Whitney J58 turbojet/ramjet engines.
- Trimethylaluminium
References
- ^ Gábor Vass, György Tarczay, Gábor Magyarfalvi, András Bödi, and László Szepes “HeI Photoelectron Spectroscopy of Trialkylaluminum and Dialkylaluminum Hydride Compounds and Their Oligomers” Organometallics, 2002, volume 21, pp. 2751–2757. doi:10.1021/om010994h
- ^ a b Michael J. Krause, Frank Orlandi, Alfred T. Saurage, Joseph R. Zietz Jr. “Aluminum Compounds, Organic” in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a01_543
- ^ Krause, M. J; Orlandi, F; Saurage, A T.; Zietz, J R, "Organic Aluminum Compounds" Wiley-Science 2002.
- ^ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-29390-6
- ^ Wataru Nagata and Yoshioka Mitsuru (1988). "Diethylaluminum Cyanides". Organic Syntheses; Collected Volumes, vol. 6, p. 436.
- ^ TEA Material Safety Data Sheet, accessed March 27, 2007
- ^ Clark, John D., Ignition! An Informal History of Liquid Rocket Propellants, Rutgers University Press, New Brunswick, NJ, 1972
- ^ Mission Status Center, June 2, 2010, 1905 GMT, SpaceflightNow, accessed 2010-06-02, Quotation: "The flanges will link the rocket with ground storage tanks containing liquid oxygen, kerosene fuel, helium, gaserous nitrogen and the first stage ignitor source called triethylaluminum-triethylborane, better known as TEA-TAB."
- ^ M202A1 Flame Assault Shoulder Weapon (Flash), inetres.com
- ^ Encyclopedia of Explosives and Related Items, Vol.8, US Army