3D model (JSmol)
|Molar mass||323.45 g·mol−1|
|Density||1.653 g cm−3|
|Melting point||−136 °C (−213 °F; 137 K)|
|Boiling point||84 to 85 °C (183 to 185 °F; 357 to 358 K) 15 mmHg|
|0.00002% (20 °C)|
|Vapor pressure||0.2 mmHg (20 °C)|
Refractive index (nD)
|R-phrases (outdated)||R61, R26/27/28, R33, R50/53, R62|
|S-phrases (outdated)||S53, S45, S60, S61|
|Flash point||73 °C (163 °F; 346 K)|
|Lethal dose or concentration (LD, LC):|
LD50 (median dose)
|35 mg/kg (rat, oral)|
17 mg/kg (rat, oral)
12.3 mg/kg (rat, oral)
LDLo (lowest published)
|30 mg/kg (rabbit, oral)|
24 mg/kg (rat, oral)
LC50 (median concentration)
|850 mg/m3 (rat, 1 hr)|
LCLo (lowest published)
|650 mg/m3 (mouse, 7 hr)|
|US health exposure limits (NIOSH):|
|TWA 0.075 mg/m3 [skin]|
|TWA 0.075 mg/m3 [skin]|
IDLH (Immediate danger)
|40 mg/m3 (as Pb)|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
TEL is a petro-fuel additive; first being mixed with gasoline (petrol) beginning in the 1920s as a patented octane rating booster that allowed engine compression to be raised substantially. This in turn caused increased vehicle performance and fuel economy. TEL had been identified chemically in the mid-19th century, but its antiknock effectiveness was discovered in 1921 by the General Motors research laboratory, which had spent several years attempting to find an additive that was both highly effective and inexpensive.
TEL levels in automotive fuel were reduced in the 1970s under the U.S. Clean Air Act in two overlapping programs: to protect catalytic converters, which mandated unleaded gasoline for those vehicles; and to protect public health, which mandated lead reductions in annual phases (the "lead phasedown"). When present in fuel, TEL is also the main cause of spark plug fouling. TEL is still used as an additive in some grades of aviation gasoline, and in some developing countries.
Innospec has claimed to be the last firm legally making TEL, and as of 2013[update] TEL is being produced illegally by several companies in China. As of March 2017, only Algeria, Yemen, and Iraq continue widespread use of leaded motor gasoline.
- 1 Synthesis and properties
- 2 Reactions
- 3 In motor fuel
- 4 Formulation of ethyl fluid
- 5 Toxicity
- 6 History
- 7 Further reading
- 8 See also
- 9 References
- 10 External links
Synthesis and properties
- 4 NaPb + 4 CH3CH2Cl → (CH3CH2)4Pb + 4 NaCl + 3 Pb
The product is recovered by steam distillation, leaving a sludge of lead and sodium chloride. TEL is a viscous colorless liquid. Because TEL is charge neutral and contains an exterior of alkyl groups, it is highly lipophilic and soluble in petrol (gasoline).
Despite decades of research, no reactions were found to improve upon this rather difficult process that involves metallic sodium and converts only 25% of the lead to TEL. A related compound, tetramethyllead, was commercially produced by a different electrolytic reaction. A process with lithium was developed but never put into practice.
A noteworthy feature of TEL is the weakness of its four C–Pb bonds. At the temperatures found in internal combustion engines, (CH3CH2)4Pb decomposes completely into lead and lead oxides as well as combustible, short-lived ethyl radicals. Lead and lead oxide scavenge radical intermediates in combustion reactions. Engine knock is caused by a cool flame, an oscillating low-temperature combustion reaction that occurs before the proper, hot ignition. Lead quenches the pyrolysed radicals and thus kills the radical chain reaction that would sustain a cool flame, preventing it from disturbing the smooth ignition of the hot flame front. Lead itself is the reactive antiknock agent, and TEL serves as a gasoline-soluble lead carrier. When (CH3CH2)4Pb burns, it produces not only carbon dioxide and water, but also lead:
- (CH3CH2)4Pb + 13 O2 → 8 CO2 + 10 H2O + Pb
This lead can oxidize further to give species such as lead(II) oxide:
- 2 Pb + O2 → 2 PbO
Pb and PbO would quickly over-accumulate and destroy an engine. For this reason, the lead scavengers 1,2-dibromoethane and 1,2-dichloroethane are used in conjunction with TEL—these agents form volatile lead(II) bromide and lead(II) chloride, respectively, which are flushed from the engine and into the air.
In motor fuel
TEL was extensively used as a gasoline additive beginning in the 1920s, wherein it served as an effective antiknock agent and prevented exhaust valve and valve seat wear. Concerns were raised in reputable journals almost immediately of likely health outcomes of fine particles of lead in the atmosphere.
Valve wear preventative
It is a common misconception that 'Tetraethyllead works as a buffer against microwelds forming between the hot exhaust valves and their seats.' Once these valves reopen, the microwelds pull apart and leave the valves with a rough surface that would abrade the seats, leading to valve recession. When lead began to be phased out of motor fuel, the automotive industry began specifying hardened valve seats and upgraded exhaust valve materials to prevent valve recession without lead.
Microwelding of the exhaust valve and valve seat is now thought to have occurred due to the increase of flame front speed when the switch to unleaded came about. The increased combustion pressures caused 'micro welding' in older style motors that had the valve seats machined into the cast iron head. Retarding the timing of the engines reduced the combustion pressures and proved to be an effective short term measure in the switch to unleaded fuel. The long term solution was hardened steel valve seats.
A gasoline-fueled reciprocating engine requires fuel of sufficient octane rating to prevent uncontrolled combustion known as engine knocking (knock or ping). Antiknock agents allow the use of higher compression ratios for greater efficiency and peak power. Adding varying amounts of additives such as low percentage TEL or high percentage ethanol to gasoline, allowed easy inexpensive control of octane ratings. TEL offered the business advantage of being commercially profitable because its use for this purpose could be patented. Aviation spirits with TEL used in WWII reached 150 octane to enable supercharged engines such as the Rolls-Royce Merlin and Griffon to reach high horsepower ratings at altitude. In military aviation, TEL manipulation allowed a range of different fuels to be tailored for particular flight conditions.
In 1935 the licence to produce TEL was given to I.G.Farben, enabling the newly formed German Luftwaffe to use high-octane gasoline. A company, Ethyl GmbH, was formed that produced TEL at two sites in Germany with a government contract from 10 June 1936.
Phaseout and ban
In most industrialized countries, a phaseout of TEL from road vehicle fuels was completed by the early 2000s because of concerns over air and soil lead levels and the accumulative neurotoxicity of lead. The use of catalytic converters, mandated in the US for 1975 and newer model-year cars to meet tighter emissions regulations, started a gradual phase-out of leaded gasoline in the US. The need for TEL was lessened by several advances in automotive engineering and petroleum chemistry. Safer methods for making higher-octane blending stocks such as reformate and iso-octane reduced the need to rely on TEL, as did other antiknock additives of varying toxicity including metallic compounds such as methylcyclopentadienyl manganese tricarbonyl (MMT) as well as oxygenates including methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE).
Lead-replacement additives were scientifically tested, and some were approved by the Federation of British Historic Vehicle Clubs at the UK's Motor Industry Research Association in 1999.
In Europe, Professor Derek Bryce-Smith was among the first to highlight the potential dangers of TEL and became a leading campaigner for removal of lead additives from petrol. However, leaded motor fuel re-entered the UK market in small quantities from 2000 in response to lobbying from classic-car organisations who contended their vehicles would be rendered useless without leaded fuel. The lead content is up to 0.15 grams per litre; Bayford & Co is the only wholesale supplier.
Vehicles designed and built to run on leaded fuel may require modification to run on unleaded gasoline or autogas. These modifications fall into two categories: those required for physical compatibility with unleaded fuel, and those performed to compensate for the relatively low octane of early unleaded fuels. Physical compatibility requires the installation of hardened exhaust valves and seats. Compatibility with reduced octane was addressed by reducing compression, generally by installing thicker cylinder head gaskets and/or rebuilding the engine with compression-reducing pistons. The availability of high-octane unleaded gasoline (or LPG) has reduced or eliminated the need to decrease compression ratios.
Leaded gasoline remained legal as of late 2014 in parts of Algeria, Iraq, Yemen, Myanmar, North Korea, and Afghanistan. It was available at the pump in most of these countries as of 2011, but very little was used in North Korea, and it was not clear whether it was sold in Afghanistan. Specialty chemical company Innospec says that it is the world's only manufacturer of TEL and sells it for automotive use nowhere except to Algeria as of late 2014. Innospec previously sold TEL to Iraq and Yemen as of 2011, but remains unclear after head executives were charged for bribing various government state-owned oil companies, to approve the sale of their TEL products. North Korea and Myanmar buy their TEL from China. The governments of Algeria and Iraq have scheduled the final elimination of leaded gasoline in their countries in 2015, after refinery upgrades. The status in Afghanistan, Yemen, and Myanmar is unclear.
In the European Union, tetraethyllead has been classified as a Substance of Very High Concern and placed on the Candidate List for Authorisation under REACH. Potential use of TEL would need to be authorised through the REACH authorisation procedure. While not a complete ban, it introduces significant obligations such as a mandatory analysis of alternatives and socioeconomic analysis.
Leaded-fuel bans for road vehicles came into effect as follows:
Leaded petrol was supposed to be completely phased out continent-wide on 1 January 2006, following a ban initiated from the 2002 Earth Summit. However, in Algeria refineries needed to be altered; as a result, leaded fuel remains available in parts of Algeria, with phaseout scheduled for 2016.
In race vehicles
Leaded fuel was commonly used in professional auto racing, until its phase out beginning in the 1990s.
NASCAR began experimentation in 1998 with an unleaded fuel, and in 2006 began switching the national series to unleaded fuel, completing the transition at the Fontana round in February 2007 when the premier class switched. This was influenced after blood tests of NASCAR teams revealed elevated blood lead levels.
TEL remains an ingredient of 100 octane avgas for piston-engine aircraft. The current formulation of 100LL (low lead, blue) aviation gasoline contains 2.12 grams of TEL per gallon, half the amount of the previous 100/130 (green) octane avgas (at 4.24 grams per gallon), but only slightly less than the 2.2 grams per gallon historically permitted in automotive leaded gasoline and substantially greater than the allowed 0.001 grams per gallon in automotive unleaded gasoline sold in the United States today. The United States Environmental Protection Agency, FAA, and others are working on economically feasible replacements for leaded avgas, which still releases 100 tons of lead every year.
Alternative antiknock agents
Antiknock agents are classed as high-percentage additives, such as alcohol, and low-percentage additives based on heavy elements. Since the main problem with TEL is its lead content, many alternative additives that contain less poisonous metals have been examined. A manganese-carrying additive, methylcyclopentadienyl manganese tricarbonyl (MMT or methylcymantrene), was used for a time as an antiknock agent, though its safety is controversial and it has been the subject of bans and lawsuits. Ferrocene, an organometallic compound of iron, is also used as an antiknock agent although with some significant drawbacks.
High-percentage additives are organic compounds that do not contain metals, but require much higher blending ratios, such as 20–30% for benzene and ethanol. It had been established by 1921 that ethanol was an effective antiknock agent, but TEL was introduced instead mainly for commercial reasons. Oxygenates such as TAME derived from natural gas, MTBE made from methanol, and ethanol-derived ETBE, have largely supplanted TEL. MTBE has environmental risks of its own and there are also bans on its use.
Improvements to gasoline itself decrease the need for antiknock additives. Synthetic iso-octane and alkylate are examples of such blending stocks. Benzene and other high-octane aromatics can be also blended to raise the octane number, but they are disfavored today because of toxicity and carcinogenicity.
Formulation of ethyl fluid
TEL was supplied for mixing with raw gasoline in the form of ethyl fluid, which was TEL blended with the lead scavengers 1,2-dibromoethane and 1,2-dichloroethane. Ethyl fluid also contained a reddish dye to distinguish treated from untreated gasoline and discourage the use of leaded gasoline for other purposes such as cleaning.
In the 1920s before safety procedures were yet developed, 17 workers for the Ethyl Corporation, DuPont, and Standard Oil died from the effects of exposure to lead.
The formula for ethyl fluid is:
Dibromoethane and dichloroethane act in a synergistic manner, where a particular mixing ratio provides the best lead scavenging ability.
Concerns over the toxicity of lead eventually led to the ban on TEL in automobile gasoline in many countries. Some neurologists have speculated that the lead phaseout may have caused average IQ levels to rise by several points in the US (by reducing cumulative brain damage throughout the population, especially in the young). For the entire US population, during and after the TEL phaseout, the mean blood lead level dropped from 16 μg/dL in 1976 to only 3 μg/dL in 1991. The US Centers for Disease Control considered blood lead levels "elevated" when they were above 10 μg/dL.
In 1853, German chemist Karl Jacob Löwig (1803–1890) first prepared what he claimed was Pb2(C2H5)3 from ethyl iodide and an alloy of lead and sodium. In 1859, English chemist George Bowdler Buckton (1818–1905) reported what he claimed was Pb(C2H5)2 from zinc ethyl (Zn(C2H5)2) and lead(II) chloride. Later authors credit both methods of preparation with producing tetraethyl lead.
TEL in fuels
Regardless of the details of the chemical discoveries, tetraethyl lead remained unimportant commercially until the 1920s. In 1921, at the direction of DuPont Corporation, which manufactured TEL, it was found to be an effective antiknock agent by Thomas Midgley, working under Charles Kettering at General Motors Corporation Research. General Motors patented the use of TEL as an antiknock agent and used the name "Ethyl" that had been proposed by Kettering in its marketing materials, thereby avoiding the negative connotation of the word "lead". Early research into "engine knocking" (also called "pinging" or "pinking") was also led by A.H. Gibson and Harry Ricardo in England and Thomas Boyd in the United States. The discovery that lead additives modified this behavior led to the widespread adoption of their use in the 1920s, and therefore more powerful, higher-compression engines. In 1924, Standard Oil of New Jersey (ESSO/EXXON) and General Motors created the Ethyl Gasoline Corporation to produce and market TEL. Deepwater, NJ across the river from Wilmington, was the site for production of some of DuPont's most important chemicals, particularly tetraethyl lead (TEL). After TEL production at the Bayway Refinery was shut down, Deepwater was the only plant in the Western hemisphere producing TEL up to 1948, when it accounted for the bulk of the Dupont/Deepwater's production.
Controversy and phase-out
The toxicity of concentrated TEL was recognized early on, as lead had been recognized since the 19th century as a dangerous substance that could cause lead poisoning. In 1924, a public controversy arose over the "loony gas", after at least 17 workers died, and many others were severely injured, in Standard and DuPont refineries in New Jersey. There had also been a private controversy for two years prior to this controversy; several public health experts, including Alice Hamilton and Yandell Henderson, engaged Midgley and Kettering with letters warning of the dangers to public health. After the death of the workers, dozens of newspapers reported on the issue. The New York Times editorialized in 1924 that the deaths should not interfere with the production of more powerful fuel.
To settle the issue, the U.S. Public Health Service conducted a conference in 1925, and the sales of TEL were voluntarily suspended for one year to conduct a hazard assessment. The conference was initially expected to last for several days, but reportedly the conference decided that evaluating presentations on alternative anti-knock agents was not "its province", so it lasted a single day. Kettering and Midgley stated that no alternatives for anti-knocking were available, although private memos showed discussion of such agents. One commonly discussed agent was ethanol. The Public Health Service created a committee that reviewed a government-sponsored study of workers and an Ethyl lab test, and concluded that while leaded gasoline should not be banned, it should continue to be investigated. The low concentrations present in gasoline and exhaust were not perceived as immediately dangerous. A U.S. Surgeon General committee issued a report in 1926 that concluded there was no real evidence that the sale of TEL was hazardous to human health but urged further study. In the years that followed, research was heavily funded by the lead industry; in 1943, Randolph Byers found children with lead poisoning had behavior problems, but he was threatened with a lawsuit and the research ended.
In the late 1920s, Robert A. Kehoe of the University of Cincinnati was the Ethyl Corporation's chief medical consultant and one of the lead industry's staunchest advocates, who would not be discredited until decades later by Dr. Clair Patterson's work on human lead burdens (see below) and other studies. In 1928, Dr. Kehoe expressed the opinion that there was no basis for concluding that leaded fuels posed any health threat. He convinced the Surgeon General that the dose–response relationship of lead had "no effect" below a certain threshold. As the head of Kettering Laboratories for many years, Kehoe would become a chief promoter of the safety of TEL, an influence that did not begin to wane until about the early 1960s. But by the 1970s, the general opinion of the safety of TEL would change, and by 1976 the U.S. government would begin to require the phaseout of this product.
In the late 1940s and early 1950s, Clair Cameron Patterson accidentally discovered the pollution caused by TEL in the environment while determining the age of the earth. As he attempted to measure lead content of very old rocks, and the time it took uranium to decay into lead, the readings were made inaccurate by lead in the environment that contaminated his samples. He was then forced to work in a cleanroom to keep his samples uncontaminated by environmental pollution of lead. After coming up with a fairly accurate estimate of the age of the earth, he turned to investigating the lead contamination problem by examining ice cores from countries such as Greenland. He realized that the lead contamination in the environment dated from about the time that TEL became widely used as a fuel additive in gasoline. Being aware of the health dangers posed by lead and suspicious of the pollution caused by TEL, he became one of the earliest and most effective opponents of its use.
In the 1970s, Herbert Needleman found that higher lead levels in children were correlated with decreased school performance. Needleman was repeatedly accused of scientific misconduct by individuals within the lead industry, but he was eventually cleared by a scientific advisory council. Needleman also wrote the average US child's blood lead level was 13.7 μg/dl in 1976 and that Patterson believed that everyone was to some degree poisoned by TEL in gasoline.
In the U.S. in 1973, the United States Environmental Protection Agency issued regulations to reduce the lead content of leaded gasoline over a series of annual phases, which therefore came to be known as the "lead phasedown" program. EPA's rules were issued under section 211 of the Clean Air Act, as amended 1970. The Ethyl Corp challenged the EPA regulations in Federal court. Although the EPA's regulation was initially dismissed, the EPA won the case on appeal, so the TEL phasedown began to be implemented in 1976. Additional regulatory changes were made by EPA over the next decade (including adoption of a trading market in "lead credits" in 1982 that became the precursor of the Acid Rain Allowance Market, adopted in 1990 for SO2), but the decisive rule was issued in 1985. Then EPA mandated that lead additive be reduced by 91 percent by the end of 1986. A 1994 study had indicated that the concentration of lead in the blood of the U.S. population had dropped 78% from 1976 to 1991. The U.S. phasedown regulations also were due in great part to studies conducted by Philip J. Landrigan.
In 1995, leaded fuel accounted for only 0.6% of total gasoline sales and less than 2000 short tons (1814 t) of lead per year. From 1 January 1996, the U.S. Clean Air Act banned the sale of leaded fuel for use in on-road vehicles. Thus, what had begun in the U.S. as a phasedown ultimately ended in a phase-out. Similar bans in other countries have resulted in lowering levels of lead in people's bloodstreams.
Taking cue from the domestic programs, the U.S. Agency for International Development undertook an initiative to reduce tetraethyl lead use in other countries, notably its efforts in Egypt begun in 1995. In 1996, with the cooperation of the U.S. AID, Egypt took almost all of the lead out of its gasoline. The success in Egypt provided a model for AID efforts worldwide.
By 2000, the TEL industry had moved the major portion of their sales to developing countries whose governments they lobbied against phasing out leaded gasoline. Leaded gasoline was withdrawn entirely from the European Union market on 1 January 2000, although it had been banned much earlier in most member states. Other countries also phased out TEL. India banned leaded petrol in March 2000.
By 2011, the United Nations announced that it had been successful in phasing out leaded gasoline worldwide. "Ridding the world of leaded petrol, with the United Nations leading the effort in developing countries, has resulted in $2.4 trillion in annual benefits, 1.2 million fewer premature deaths, higher overall intelligence and 58 million fewer crimes," the United Nations Environmental Programme said. The announcement was slightly premature, as a few countries still have leaded gasoline for sale as of 2013 (see above).
Effect on crime rates
A statistically significant correlation has been found between the usage rate of leaded gasoline and violent crime: the violent crime curve virtually tracks the lead exposure curve with a 22-year time lag. After the ban on TEL, blood lead levels in US children dramatically decreased.
Reduction in the average blood lead level is believed to have been a major cause for falling violent crime rates in the United States and South Africa. Researchers including Amherst College economist Jessica Wolpaw Reyes, Department of Housing and Urban Development consultant Rick Nevin, and Howard Mielke of Tulane University say that declining exposure to lead is responsible for an up to 56% decline in crime from 1992 to 2002. Taking into consideration other factors that are believed to have increased crime rates over that period, Reyes found that the reduced exposure to lead led to an actual decline of 34% over that period.
Although leaded gasoline is largely gone in North America, it has left high concentrations of lead in the soil adjacent to roads that were heavily used prior to its phaseout. Children are particularly at risk if they consume this.
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- George Bowdler Buckton (1859) "Further remarks on the organo-metallic radicals, and observations more particularly directed to the isolation of mercuric, plumbic, and stannic ethyl," Proceedings of the Royal Society of London, 9 : 309-316. For Buckton's preparation of tetraethyl lead, see pages 312-314.
- See, for example:
- H. E. Roscoe and C. Schorlemmer, A Treatise on Chemistry, Volume 3, Part 1 (New York, New York: D. Appleton and Co., 1890), page 466.
- Frankland and Lawrence credit Buckton with synthesizing tetraethyl lead in: E. Frankland and Awbrey Lawrance (1879) "On plumbic tetrethide," Journal of the Chemical Society, Transactions, 35 : 244-249.
- "Leaded Gasoline, Safe Refrigeration, and Thomas Midgley, Jr." Chapter 6 in S. Bertsch McGrayne. Prometheans in the Lab. McGraw-Hill: New York, 2002. ISBN 0-07-140795-2
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- Bryson, Christopher (2004). The Fluoride Deception, p. 41. Seven Stories Press. Citing historian Lynne Snyder.
- Bryson, B. (2003). "10. Getting the Lead Out". A Short History of Nearly Everything. New York: Broadway Books. ISBN 978-0-7679-0818-4.
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- "Lead Credit Trading". National Center for Environmental Economics. US EPA. c. 2006. Retrieved 3 October 2014.
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- Schnaas, Lourdes; Rothenberg, Stephen J.; Flores, María-Fernanda; Martínez, Sandra; Hernández, Carmen; Osorio, Erica; Perroni, Estela (2004). "Blood Lead Secular Trend in a Cohort of Children in Mexico City (1987–2002)". Environ. Health Perspect. 112 (10): 1110–1115. doi:10.1289/ehp.6636. PMC 1247386. PMID 15238286.
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- Valerie Franchi, "Getting the Lead Out," Front Lines, published by the U.S. Agency for International Development, Oct. 1997.
- "The Case for Banning Lead in Gasoline" (PDF). Manufacturers of Emission Controls Association (MECA). January 2003. Archived from the original (PDF) on 26 April 2012. Retrieved 7 June 2012.
- "Phase-out of leaded petrol brings huge health and cost benefits". 27 October 2011.
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- Lean, Geoffrey (27 October 2007). "Ban on leaded petrol 'has cut crime rates around the world'". The Independent.
- Matthews, Dylan (22 April 2013). "Lead abatement, alcohol taxes and 10 other ways to reduce the crime rate without annoying the NRA". Washington Post. Retrieved 23 May 2013.
- Marrs, Dave (22 January 2013). "Ban on lead may yet give us respite from crime". Business Day. Retrieved 23 May 2013.
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- Drum, Kevin (January–February 2013). "America's Real Criminal Element: Lead". Mother Jones. Retrieved 4 January 2013.
- U.S. Gov't, National Institute for Occupational Safety and Health. NIOSH Pocket Guide to Chemical Hazards
- Kovarik, Bill (1999). Charles F. Kettering and the 1921 Discovery of Tetraethyl Lead
- True unleaded alternative for 100LL needed for general aviation