Tetraethyl lead: Difference between revisions
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| align="left"|'''[[Boiling point]]''' || align="left"|455.7 K (182.6 °C) at 1 atm<ref name=NIST/> | | align="left"|'''[[Boiling point]]''' || align="left"|455.7 K (182.6 °C) at 1 atm<ref name=NIST/> | ||
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| align="left"|'''Melting point''' || align="left"|142.94 K (-130.2 °C)<ref name=NIST/> | | align="left"|'''[[Melting point]]''' || align="left"|142.94 K (-130.2 °C)<ref name=NIST/> | ||
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| align="left"|'''Flash point'''|| align="left"|366.48 K (93.3 °C)<ref name=NOAA/> | | align="left"|'''[[Flash point]]'''|| align="left"|366.48 K (93.3 °C)<ref name=NOAA/> | ||
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| align="left"|'''[[Specific heat]], c<sub>p</sub>''' || align="left"|0.956 J/(g·K) for liquid at 20 °C<ref name=NIST/> | | align="left"|'''[[Specific heat]], c<sub>p</sub>''' || align="left"|0.956 J/(g·K) for liquid at 20 °C<ref name=NIST/> | ||
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| align="left"|'''Heat of vaporization'''|| align="left"|175.0 J/g for liquid at 182.6 °C<ref name=NIST/> | | align="left"|'''[[Heat of vaporization]]'''|| align="left"|175.0 J/g for liquid at 182.6 °C<ref name=NIST/> | ||
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| align="left"|'''Heat of fusion'''|| align="left"|27.2 J/g for solid at -130.2 °C<ref name=NIST/> | | align="left"|'''[[Heat of fusion]]'''|| align="left"|27.2 J/g for solid at -130.2 °C<ref name=NIST/> | ||
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| align="left"|'''Viscosity'''||align="left"|0.862 mPa·s (0.862 cP) at 20 °C<ref>[http://cameochemicals.noaa.gov/chris/TEL.pdf Tetraethyl lead] From the website of the National Oceanic and Atmospheric Administration (NOAA)</ref> | | align="left"|'''[[Viscosity]]'''||align="left"|0.862 mPa·s (0.862 cP) at 20 °C<ref>[http://cameochemicals.noaa.gov/chris/TEL.pdf Tetraethyl lead] From the website of the National Oceanic and Atmospheric Administration (NOAA)</ref> | ||
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| align="left"|'''Refractive index'''||align="left"|1.5198 ''n''<sub>D</sub><sup>20 </sup><ref>{{cite book| author=Béla G. Lipták|title=Instrument Engineers' Handbook|edition=4th Edition|publisher=CRC Press|year=2003|id=0-8493-1083-0}}</ref> | | align="left"|'''[[Refractive index]]'''||align="left"|1.5198 ''n''<sub>D</sub><sup>20 </sup><ref>{{cite book| author=Béla G. Lipták|title=Instrument Engineers' Handbook|edition=4th Edition|publisher=CRC Press|year=2003|id=0-8493-1083-0}}</ref> | ||
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Revision as of 16:25, 11 February 2010
Tetraethyl lead (TEL) is a liquid with the chemical formula (CH3CH2)4Pb. Once widely used (circa 1925 to 1990) to increase the octane rating of gasoline (petrol), TEL usage in gasoline has been largely phased out by most nations[1] primarily because of the toxicity of the lead emissions from spark-ignited internal combustion engines burning gasoline containing TEL. Another reason for discontinuing TEL usage was that it degraded the efficiency of the catalytic converters installed in automotive vehicles to reduce their emissions of air pollutants.
Manufacture and properties
TEL is produced by the alkylation of a sodium-lead alloy using chloroethane as expressed by this chemical equation:
- 4 CH3CH2Cl + 4 NaPb → (CH3CH2)4Pb + 4 NaCl + 3 Pb
which can also be written as:
- 4 moles of chloroethane + 4 moles of sodium-lead alloy → 1 mole of tetraethyl lead + 4 moles of sodium chloride + 3 moles of lead
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The product tetraethyl lead is a viscous colorless liquid that is highly lipophilic and soluble in fats, oils and lipids as well as gasoline and other non-polar hydrocarbons. Other properties of tetraethyl lead are listed in the adjacent table.
At the temperatures found in spark-ignited internal combustion engines, TEL decomposes completely into lead and lead oxide (PbO) and combustible, short-lived ethyl radicals. Lead itself is the reactive agent that enhances the octane rating of gasolines and tetraethyl lead serves as a gasoline-soluble lead carrier.
TEL fluid formulation
When TEL burns, it produces not only carbon dioxide (CO2) and water (H2O), but also lead (Pb):
- (CH3CH2)4Pb + 13 O2 → 8 CO2 + 10 H2O + Pb
The lead can the oxidize further to give lead oxide (PbO):
- 2 Pb + O2 → 2 PbO
The Pb and PbO would soon accumulate and destroy an engine. For this reason, the TEL used in gasoline was actually part of a blended liquid formulation known as TEL fluid or ethyl fluid that contained 1,2-dibromoethane and 1,2-dichloroethane liquids known as lead scavengers. Those scavengers formed lead bromide (PbBr) and lead chloride (PbCl) which are volatile and were emitted from the engine exhaust to the atmosphere. The complete composition of TEL fluid was:[6]
- Tetraethyl lead 61.45%
- 1,2-Dibromoethane 17.85%
- 1,2-Dichloroethane 18.80%
- Inerts & color dye 1.90%
The addition of as little as 0.8 ml of TEL fluid per liter of gasoline (3 ml/gallon) of gasoline was equivalent to adding 0.5 g of lead per liter of gasoline and resulted in significant increases in the octane rating of the gasoline.
History of tetraethyl lead as a gasoline octane enhancer
Good sources for TEL history.[7] [8]
References
- ↑ Phasing Lead Out of Gasoline A report issued by the United Nations Environmental Programme (UNEP). See page 8 of 23 pdf pages.
- ↑ 2.0 2.1 2.2 2.3 2.4 2.5 NIST Chemistry WebBook
- ↑ 3.0 3.1 Tetraethyl lead, liquid] From the website of the National Oceanic and Atmospheric Administration (NOAA)
- ↑ Tetraethyl lead From the website of the National Oceanic and Atmospheric Administration (NOAA)
- ↑ Béla G. Lipták (2003). Instrument Engineers' Handbook, 4th Edition. CRC Press. 0-8493-1083-0.
- ↑ Historical Uses A publication of the U.S. Environmental Protection Agency
- ↑ The Rise and Fall of Tetraethyllead. 2. Dietmar Seyferth, Department of Chemistry, Massachusetts Institute of Technology, Organometallics, 2003, 22 (25), pp 5154–5178
- ↑ Charles F. Kettering and the 1921 Discovery of Tetraethyl Lead In the Context of Technological Alternatives