Tetraethyllead (commonly styled tetraethyl lead), abbreviated TEL, is an
organolead compound with the formula
Pb(
C2H5)
4. It is a
fuel
A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work. The concept was originally applied solely to those materials capable of releasing chemical energy bu ...
additive, first being mixed with
gasoline
Gasoline (; ) or petrol (; ) (see ) is a transparent, petroleum-derived flammable liquid that is used primarily as a fuel in most spark-ignited internal combustion engines (also known as petrol engines). It consists mostly of organic ...
beginning in the 1920s as a patented
octane rating booster that allowed
engine compression to be raised substantially. This in turn increased vehicle performance and fuel economy.
TEL was first
synthesised by German chemist
Carl Jacob Löwig in 1853. American
chemical engineer
In the field of engineering, a chemical engineer is a professional, equipped with the knowledge of chemical engineering, who works principally in the chemical industry to convert basic raw materials into a variety of products and deals with the ...
Thomas Midgley Jr., who was working for
General Motors, was the first to discover its effectiveness as an
antiknock agent in 1921, after spending several years attempting to find an
additive that was both highly effective and inexpensive.
Concerns were later raised over the toxic effects of
lead
Lead is a chemical element with the Symbol (chemistry), symbol Pb (from the Latin ) and atomic number 82. It is a heavy metals, heavy metal that is density, denser than most common materials. Lead is Mohs scale of mineral hardness#Intermediate ...
, especially on children.
On cars not designed to operate on leaded gasoline, lead and lead oxides coat the catalyst in
catalytic converter
A catalytic converter is an exhaust emission control device that converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalyzing a redox reaction. Catalytic converters are usuall ...
s, rendering them ineffective, and can sometimes foul
spark plug
A spark plug (sometimes, in British English, a sparking plug, and, colloquially, a plug) is a device for delivering electric current from an ignition system to the combustion chamber of a spark-ignition engine to ignite the compressed fuel/air ...
s. Starting in the 1970s, many countries began phasing out TEL in automotive fuel. In 2011 a study, backed by the United Nations, estimated that the removal of TEL had resulted in $2.4 trillion in annual benefits, and 1.2 million fewer premature deaths.
TEL is still used as an additive in some grades of
aviation fuel
Aviation fuels are petroleum-based fuels, or petroleum and synthetic fuel blends, used to power aircraft. They have more stringent requirements than fuels used for ground use, such as heating and road transport, and contain additives to enhance ...
.
Innospec has claimed to be the last firm legally making TEL but, , TEL was being produced illegally by several companies in China.
In July 2021, the sale of leaded gasoline for cars was completely phased out worldwide, prompting the
United Nations Environment Programme
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the United Nations Conference on ...
(UNEP) to declare an "official end" of its use in cars on August 30, 2021.
Synthesis and properties
TEL is produced by reacting
chloroethane with a
sodium
Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable ...
–
lead
Lead is a chemical element with the Symbol (chemistry), symbol Pb (from the Latin ) and atomic number 82. It is a heavy metals, heavy metal that is density, denser than most common materials. Lead is Mohs scale of mineral hardness#Intermediate ...
alloy
An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductilit ...
.
The product is recovered by steam distillation, leaving a sludge of lead and sodium chloride. TEL is a
viscous colorless
liquid
A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, an ...
with a sweet odor. Because TEL is charge neutral and contains an exterior of alkyl groups, it is highly
lipophilic and soluble in petrol (gasoline). This property, which allows it to dissolve so evenly and effectively in motor fuel also allows it to diffuse through the blood–brain barrier, and accumulate within the limbic forebrain, frontal cortex, and hippocampus.
Despite decades of research, no reactions were found to improve upon this process that is rather difficult, 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
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid ...
was developed but never put into practice.
Reactions
A noteworthy feature of TEL is the weakness of its four C–Pb bonds. At the temperatures found in
internal combustion engine
An internal combustion engine (ICE or IC engine) is a heat engine in which the combustion of a fuel occurs with an oxidizer (usually air) in a combustion chamber that is an integral part of the working fluid flow circuit. In an internal co ...
s, TEL decomposes completely into lead as well as combustible, short-lived ethyl
radicals
Radical may refer to:
Politics and ideology Politics
*Radical politics, the political intent of fundamental societal change
*Radicalism (historical), the Radical Movement that began in late 18th century Britain and spread to continental Europe and ...
. Lead and lead oxide scavenge
radical intermediates in
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combust ...
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 the ethyl groups serve as a gasoline-soluble carrier.
When TEL burns, it produces not only carbon dioxide and water, but also lead and lead(II) oxide:
[
:
:
Pb and PbO would quickly over-accumulate and foul an engine. For this reason, ]1,2-dichloroethane
The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vin ...
and 1,2-dibromoethane were also added to gasoline as lead scavengers—these agents form volatile lead(II) chloride and lead(II) bromide, respectively, which flush the lead 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 reduced exhaust valve
A valve is a device or natural object that regulates, directs or controls the flow of a fluid (gases, liquids, fluidized solids, or slurries) by opening, closing, or partially obstructing various passageways. Valves are technically fitting ...
and valve seat wear. Concerns were raised in reputable journals of likely health outcomes of fine particles of lead in the atmosphere.
Valve wear preventive
Tetraethyllead helped cool intake valves and was an excellent buffer against microwelds forming between exhaust valves and their seats. Once these valves reopen, the microwelds pull apart and abrade the valves and seats, leading to valve recession. When TEL began to be phased out, the automotive industry began specifying hardened valve seats and upgraded materials which allow for high wear resistance without requiring lead.
Antiknock agent
A gasoline-fuelled reciprocating engine requires fuel of sufficient octane rating to prevent uncontrolled combustion (preignition and detonation
Detonation () is a type of combustion involving a supersonic exothermic front accelerating through a medium that eventually drives a shock front propagating directly in front of it. Detonations propagate supersonically through shock waves with ...
). Antiknock agents allow the use of higher compression ratio
The compression ratio is the ratio between the volume of the cylinder and combustion chamber in an internal combustion engine at their maximum and minimum values.
A fundamental specification for such engines, it is measured two ways: the stat ...
s for greater efficiency and peak power. Adding varying amounts of additives 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 fuels with TEL used in WWII reached octane ratings of 150 to enable turbocharged and supercharged engines such as the Rolls-Royce Merlin
The Rolls-Royce Merlin is a British liquid-cooled V-12 piston aero engine of 27- litres (1,650 cu in) capacity. Rolls-Royce designed the engine and first ran it in 1933 as a private venture. Initially known as the PV-12, it was later ...
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 a licence to produce TEL was given to IG Farben
Interessengemeinschaft Farbenindustrie AG (), commonly known as IG Farben (German for 'IG Dyestuffs'), was a German chemical and pharmaceutical conglomerate. Formed in 1925 from a merger of six chemical companies— BASF, Bayer, Hoechst, Agfa ...
, enabling the newly formed German 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.
In 1938 the United Kingdom Air Ministry
The Air Ministry was a department of the Government of the United Kingdom with the responsibility of managing the affairs of the Royal Air Force, that existed from 1918 to 1964. It was under the political authority of the Secretary of State ...
contracted with ICI for the construction and operation of a TEL plant. A site was chosen at Holford Moss, near Plumley in Cheshire. Construction started in April 1939 and TEL was being produced by September 1940.
"Ethyl Fluid"
For mixing with raw gasoline, TEL was most commonly supplied in the form of "Ethyl Fluid", which consisted of TEL blended with 1,2-dichloroethane and 1,2-dibromoethane. 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 strengthened, 17 workers for the Ethyl Corporation, DuPont, and Standard Oil
Standard Oil Company, Inc., was an American oil production, transportation, refining, and marketing company that operated from 1870 to 1911. At its height, Standard Oil was the largest petroleum company in the world, and its success made its co- ...
died from the effects of exposure to lead.
Ethyl Fluid's formulation consisted of:
* 61.45% Tetraethyllead
* 18.80% 1,2-Dichloroethane
The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vin ...
* 17.85% 1,2-Dibromoethane
* 1.90% Inerts and dyes
Dichloroethane and dibromoethane act in a synergistic manner, where equal or approximately equal quantities of both provide the best scavenging ability.
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. 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
The authorisation procedure is one of the regulatory tools of the European regulation (EC) REACH n°1907/2006 aiming to ban the use of substances of very high concern (SVHC) included in the Annex XIV of REACH, so as to replace them with technica ...
. While not a complete ban, it introduces significant obligations such as a mandatory analysis of alternatives and socioeconomic analysis.
The use of catalytic converter
A catalytic converter is an exhaust emission control device that converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalyzing a redox reaction. Catalytic converters are usuall ...
s, mandated in the United States for 1975 and later model-year cars to meet tighter emissions regulations, started a gradual phase-out of leaded gasoline in the U.S. 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
2,2,4-Trimethylpentane, also known as isooctane or iso-octane, is an organic compound with the formula (CH3)3CCH2CH(CH3)2. It is one of several isomers of octane (C8H18). This particular isomer is the standard 100 point on the octane rating scale ...
reduced the need to rely on TEL, as did other antiknock additives of varying toxicity including metallic compounds such as methylcyclopentadienyl manganese tricarbonyl
Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (C5H4CH3)Mn(CO)3. Initially marketed as a supplement for use in leaded gasoline, MMT was later used in unleaded gasoline to increase the o ...
(MMT) as well as oxygenates including methyl tertiary-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. Bayford & Co was the only wholesale supplier.
Vehicles designed and built to run on leaded fuel often require modification to run on unleaded gasoline. 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, although modern high-octane unleaded gasoline has eliminated the need to decrease compression ratios.
Leaded gasoline remained legal as of late 2014 in parts of Algeria
)
, image_map = Algeria (centered orthographic projection).svg
, map_caption =
, image_map2 =
, capital = Algiers
, coordinates =
, largest_city = capital
, religi ...
, Iraq
Iraq,; ku, عێراق, translit=Êraq officially the Republic of Iraq, '; ku, کۆماری عێراق, translit=Komarî Êraq is a country in Western Asia. It is bordered by Turkey to Iraq–Turkey border, the north, Iran to Iran–Iraq ...
, Yemen
Yemen (; ar, ٱلْيَمَن, al-Yaman), officially the Republic of Yemen,, ) is a country in Western Asia. It is situated on the southern end of the Arabian Peninsula, and borders Saudi Arabia to the north and Oman to the northeast an ...
, Myanmar
Myanmar, ; UK pronunciations: US pronunciations incl. . Note: Wikipedia's IPA conventions require indicating /r/ even in British English although only some British English speakers pronounce r at the end of syllables. As John Wells explai ...
, North Korea
North Korea, officially the Democratic People's Republic of Korea (DPRK), is a country in East Asia. It constitutes the northern half of the Korean Peninsula and shares borders with China and Russia to the north, at the Yalu (Amnok) and ...
, and Afghanistan
Afghanistan, officially the Islamic Emirate of Afghanistan,; prs, امارت اسلامی افغانستان is a landlocked country located at the crossroads of Central Asia and South Asia. Referred to as the Heart of Asia, it is bord ...
. North Korea and Myanmar purchased their TEL from China, while Algeria, Iraq, and Yemen purchased it from the specialty chemical company Innospec, the world's sole remaining legal manufacturer of TEL. In 2011 several Innospec executives were charged and imprisoned for bribing various government state-owned oil companies to approve the sale of their TEL products.
the UNEP
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the United Nations Conference on ...
-sponsored phase-out was nearly complete: only Algeria, Iraq, and Yemen continued widespread use of leaded gasoline, although not exclusively. In July 2021, Algeria—the last country to sell leaded gasoline—had halted its sale.
Leaded-fuel bans
Leaded-fuel bans for road vehicles came into effect as follows:
= Europe
=
*Austria: 1989
*Bosnia and Herzegovina: 2009
*Croatia: 2006
*Czech Republic: 2001
*Denmark: 1994
*European Union
The European Union (EU) is a supranational political and economic union of member states that are located primarily in Europe. The union has a total area of and an estimated total population of about 447million. The EU has often been ...
: 1 January 2000
*Finland: 1994
*France: 2000
*Germany: 1996
*Gibraltar: 2001
*Greece: 2002
*Hungary: 1999
*Ireland: 1 January 2000
*Italy: 1 January 2002
*Monaco: 2000
*Netherlands: 1998
*Norway: 1997
*Poland: December 2000
*Slovenia: 2001
*Spain: 1 August 2001
*Portugal: 1999
*Romania: 2005
*Russia: 2003
*Serbia: 2010
*Sweden: 1995
*Switzerland: 2000
*Ukraine: 2003
*United Kingdom: 1 January 2000
= North America
=
*Antigua and Barbuda: 1991
*Canada: December 1990
*United States (including Puerto Rico): 1 January 1996
**California: 1992
*Bahamas: 1996
*Belize: 1997
*Bermuda: 1990
*Costa Rica: 1996
*Dominican Republic: 1999
*El Salvador: 1992
*Guatemala: 1991
*Haiti: 1998
*Honduras: 1996
*Mexico: 1998
*Nicaragua: 1995
*Panama: 2002
*Trinidad and Tobago: 2000
= South America
=
*Argentina: 1998
*Bolivia: 1995
*Brazil: 1989 or 1991
*Chile: 2001 or 2005
*Colombia: 1991
*Guyana: 2000
*Peru: 2004
*Suriname: 2001
*Uruguay: 2004
*Venezuela: 2005
= Asia
=
*Afghanistan: 2016
*Bangladesh: 1999
*China: 2000
*Hong Kong: 1999
*India: March 2000
*Saudi Arabia: 2001
*Indonesia: 2006
*Iran: 2003
*Iraq: 2018[https://wedocs.unep.org/bitstream/handle/20.500.11822/25422/MapWorldLead_March2018.pdf?sequence=1&isAllowed=y ][https://wedocs.unep.org/bitstream/handle/20.500.11822/25756/MapWorldLead_July2018.pdf?sequence=1&isAllowed=y ]
*Japan: 1986
*Malaysia: 2000
*Myanmar: 2016
*Nepal: 2000
*North Korea: 2016
*Pakistan: 2001
*Philippines: 2000
*Singapore: 1998
*South Korea: 1993
*Sri Lanka: 1999
*Taiwan: 2000
*Thailand: 1996
*Turkey: 2006
*United Arab Emirates: 2003
*Vietnam: 2001
*Yemen: 2018
= Oceania
=
*Australia: 2002
*New Zealand: 1996
*Guam: 1 January 1996 (USA)
= Africa
=
*Egypt: 1999
*South Africa: 2006
*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 remained available in parts of Algeria
)
, image_map = Algeria (centered orthographic projection).svg
, map_caption =
, image_map2 =
, capital = Algiers
, coordinates =
, largest_city = capital
, religi ...
, with phaseout scheduled for 2016. After the Algerian Government outlawed the sale of leaded petrol throughout all of Algeria, leaded petrol has now been effectively phased out.
In motor racing
Leaded fuel was commonly used in professional motor racing
Motorsport, motorsports or motor sport is a global term used to encompass the group of competitive sporting events which primarily involve the use of motorized vehicles. The terminology can also be used to describe forms of competition of tw ...
, until its phase out beginning in the 1990s. Since 1993, Formula One
Formula One (also known as Formula 1 or F1) is the highest class of international racing for open-wheel single-seater formula racing cars sanctioned by the Fédération Internationale de l'Automobile (FIA). The World Drivers' Championship ...
racing cars have been required to use fuel containing no more than 5 mg/L of lead.
NASCAR
The National Association for Stock Car Auto Racing, LLC (NASCAR) is an American auto racing sanctioning and operating company that is best known for stock car racing. The privately owned company was founded by Bill France Sr. in 1948, and h ...
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.
Aviation gasoline
TEL remains an ingredient of 100 octane avgas
Avgas (aviation gasoline, also known as aviation spirit in the UK) is an aviation fuel used in aircraft with spark-ignited internal combustion engines. ''Avgas'' is distinguished from conventional gasoline (petrol) used in motor vehicles, w ...
for piston-engine aircraft. The current formulation of 100LL (low lead, blue) aviation gasoline contains of TEL, half the amount of the previous 100/130 (green) octane avgas (at 4.24 grams per gallon), and twice as much as the 1 gram per gallon permitted in regular automotive leaded gasoline prior to 1988 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. Children living near airports servicing small (piston-engine) aircraft have measurably higher concentrations of lead in their blood.
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
Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (C5H4CH3)Mn(CO)3. Initially marketed as a supplement for use in leaded gasoline, MMT was later used in unleaded gasoline to increase the o ...
(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
Ferrocene is an organometallic compound with the formula . The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, ...
, an organometallic
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and ...
compound of iron
Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
, is also used as an antiknock agent although with some significant drawbacks.
High-percentage additives are organic compound
In chemistry, organic compounds are generally any chemical compounds that contain carbon- hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. Th ...
s that do not contain metals, but require much higher blending ratios, such as 20–30% for benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen ato ...
and ethanol
Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a h ...
. 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
Methyl ''tertiary''-butyl ether (MTBE), also known as methyl tert-butyl ether and ''tert''-butyl methyl ether, is an organic compound with a structural formula (CH3)3COCH3. MTBE is a volatile, flammable, and colorless liquid that is sparingly sol ...
made from methanol, and ethanol-derived ETBE
Ethyl ''tertiary''-butyl ether (ETBE), also known as ethyl ''tert''-butyl ether, is commonly used as an oxygenate gasoline additive in the production of gasoline from crude oil. ETBE offers equal or greater air quality benefits than ethan ...
, 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
2,2,4-Trimethylpentane, also known as isooctane or iso-octane, is an organic compound with the formula (CH3)3CCH2CH(CH3)2. It is one of several isomers of octane (C8H18). This particular isomer is the standard 100 point on the octane rating scale ...
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
Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a subs ...
and carcinogen
A carcinogen is any substance, radionuclide, or radiation that promotes carcinogenesis (the formation of cancer). This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes. Several radioactive subst ...
icity.
Toxicity
Tetraethyllead is highly toxic, with as little as 6 mL being enough to induce severe lead poisoning
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. The brain is the most sensitive. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, inferti ...
. The hazards of TEL's lead content are heightened due to the compound's volatility and high lipophilicity
Lipophilicity (from Greek λίπος "fat" and φίλος "friendly"), refers to the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such non-polar solvents are themselves lipo ...
, enabling it to easily cross the blood–brain barrier and accumulate in the limbic system
The limbic system, also known as the paleomammalian cortex, is a set of brain structures located on both sides of the thalamus, immediately beneath the medial temporal lobe of the cerebrum primarily in the forebrain.Schacter, Daniel L. 2012. ' ...
, frontal cortex
The frontal lobe is the largest of the four major lobes of the brain in mammals, and is located at the front of each cerebral hemisphere (in front of the parietal lobe and the temporal lobe). It is parted from the parietal lobe by a groove ...
, and hippocampus
The hippocampus (via Latin from Greek , ' seahorse') is a major component of the brain of humans and other vertebrates. Humans and other mammals have two hippocampi, one in each side of the brain. The hippocampus is part of the limbic system, ...
, making chelation therapy
Chelation therapy is a medical procedure that involves the administration of chelating agents to remove heavy metals from the body. Chelation therapy has a long history of use in clinical toxicology and remains in use for some very specific medi ...
ineffective.
Early symptoms of acute exposure to tetraethyllead can manifest as irritation of the eyes and skin, sneezing, fever, vomiting, and a metallic taste in the mouth. Later symptoms of acute TEL poisoning include pulmonary edema
Pulmonary edema, also known as pulmonary congestion, is excessive liquid accumulation in the tissue and air spaces (usually alveoli) of the lungs. It leads to impaired gas exchange and may cause hypoxemia and respiratory failure. It is du ...
, anemia
Anemia or anaemia (British English) is a blood disorder in which the blood has a reduced ability to carry oxygen due to a lower than normal number of red blood cells, or a reduction in the amount of hemoglobin. When anemia comes on slowly, ...
, ataxia, convulsions, severe weight loss, delirium
Delirium (also known as acute confusional state) is an organically caused decline from a previous baseline of mental function that develops over a short period of time, typically hours to days. Delirium is a syndrome encompassing disturbances ...
, irritability, hallucinations, nightmares, fever, muscle and joint pain, swelling of the brain, coma, and damage to cardiovascular and renal organs.
Chronic exposure to TEL can cause long-term negative effects such as memory loss, delayed reflexes, neurological problems, insomnia, tremors, psychosis, loss of attention, and an overall decrease in IQ and cognitive function.
The carcinogenity
A carcinogen is any substance, radionuclide, or radiation that promotes carcinogenesis (the formation of cancer). This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes. Several radioactive subs ...
of tetraethyllead is debatable. It is believed to harm the male reproductive system and cause birth defects.
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 U.S. Centers of Disease control previously labelled children with 10 µg/dL or more as having a "blood lead level of concern." In 2021, the level was lowered in accordance with the average lead level in the U.S. decreasing to 3.5 µg/dL or more as having a "blood lead level of concern."
History
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
George Bowdler Buckton (24 May 1818, London – 25 September 1905, Haslemere, Surrey) was an English chemist and entomologist who specialised in aphids.
Early Life
Buckton was born in London and lived in Hornsey, England. He was the eldest so ...
(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.
In fuel
Regardless of the details of the chemical discoveries, tetraethyl lead remained unimportant commercially until the 1920s.[Kitman, J. (2 March 2000)]
"The Secret History of Lead."
''The Nation
''The Nation'' is an American liberal biweekly magazine that covers political and cultural news, opinion, and analysis. It was founded on July 6, 1865, as a successor to William Lloyd Garrison's ''The Liberator'', an abolitionist newspaper tha ...
''. Retrieved 17 August 2009. 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
The General Motors Company (GM) is an American Multinational corporation, multinational Automotive industry, automotive manufacturing company headquartered in Detroit, Michigan, United States. It is the largest automaker in the United States and ...
Research. General Motors patent
A patent is a type of intellectual property that gives its owner the legal right to exclude others from making, using, or selling an invention for a limited period of time in exchange for publishing an sufficiency of disclosure, enabling disclo ...
ed 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
In spark ignition internal combustion engines, knocking (also knock, detonation, spark knock, pinging or pinking) occurs when combustion of some of the air/fuel mixture in the cylinder does not result from propagation of the flame front igni ...
" (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
Lead is a chemical element with the Symbol (chemistry), symbol Pb (from the Latin ) and atomic number 82. It is a heavy metals, heavy metal that is density, denser than most common materials. Lead is Mohs scale of mineral hardness#Intermediate ...
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, New Jersey, across the river from Wilmington, was the site for production of some of DuPont's most important chemicals, particularly 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.
Initial controversy
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
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. The brain is the most sensitive. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, inferti ...
. In 1924, a public controversy arose over the "loony gas", after five workers died, and many others were severely injured, in Standard Oil 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
Yandell Henderson (April 23, 1873 – February 18, 1944) was an American physiologist.
West, John B. (1988"Yandell Henderson"in ''Biographical Memoirs'' Vol. 74. American Academies Press , 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 Randolph may refer to:
Places In the United States
* Randolph, Alabama, an unincorporated community
* Randolph, Arizona, a populated place
* Randolph, California, a village merged into the city of Brea
* Randolph, Illinois, an unincorporated commu ...
found children with lead poisoning had behavior problems, but the Lead Industries Association threatened him with a lawsuit and the research ended.
In the late 1920s, Robert A. Kehoe
Robert Arthur Kehoe (; November 18, 1893 – November 24, 1992) was an American toxicologist and a dominant figure in occupational health. Working on behalf of the lead industry (including the manufacturing of leaded gasoline and lead-acid batter ...
of the University of Cincinnati
The University of Cincinnati (UC or Cincinnati) is a public research university in Cincinnati, Ohio. Founded in 1819 as Cincinnati College, it is the oldest institution of higher education in Cincinnati and has an annual enrollment of over 44,00 ...
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
The age of Earth is estimated to be 4.54 ± 0.05 billion years This age may represent the age of Earth's accretion, or core formation, or of the material from which Earth formed. This dating is based on evidence from radiometric age-dating of ...
. 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
A cleanroom or clean room is an engineered space, which maintains a very low concentration of airborne particulates. It is well isolated, well-controlled from contamination, and actively cleansed. Such rooms are commonly needed for scientif ...
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
Greenland ( kl, Kalaallit Nunaat, ; da, Grønland, ) is an island country in North America that is part of the Kingdom of Denmark. It is located between the Arctic and Atlantic oceans, east of the Canadian Arctic Archipelago. Greenland is ...
. 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 proponents of removing it from use.
In the 1960s, the first clinical works were published proving the toxicity of this compound in humans, e.g. by Mirosław Jan Stasik.
Modern findings
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
The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it ...
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 invalidated, 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
Philip John Landrigan (born June 14, 1942), is an American epidemiologist and pediatrician and one of the world's leading advocates of children's health.
His work has been recognized by national non-profit organization Healthy Child Healthy Wor ...
.
From 1 January 1996, the U.S. Clean Air Act banned the sale of leaded fuel for use in on-road vehicles although that year the US EPA indicated that TEL could still be used in aircraft, racing cars, farm equipment, and marine engines. Thus, what had begun in the U.S. as a phasedown ultimately ended in a phase-out for on-road vehicle TEL. Similar bans in other countries have resulted in lowering levels of lead in people's blood
Blood is a body fluid in the circulatory system of humans and other vertebrates that delivers necessary substances such as nutrients and oxygen to the cells, and transports metabolic waste products away from those same cells. Blood in th ...
streams.
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
India, officially the Republic of India ( Hindi: ), is a country in South Asia. It is the seventh-largest country by area, the second-most populous country, and the most populous democracy in the world. Bounded by the Indian Ocean on the ...
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 2017. On 30 August 2021 the United Nations Environment Programme
The United Nations Environment Programme (UNEP) is responsible for coordinating responses to environmental issues within the United Nations system. It was established by Maurice Strong, its first director, after the United Nations Conference on ...
announced that leaded gasoline had been eliminated. The final stocks of the product were used up in Algeria, which had continued to produce leaded gasoline until July 2021.
Effect on crime rates
Reduction in the average blood lead level is believed to have been a major cause for falling violent crime rates in the United States. 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.[Reyes, J. W. (2007)]
"The Impact of Childhood Lead Exposure on Crime". National Bureau of Economic Research.
"a" ref citing Pirkle, Brody, et. al (1994). Retrieved 17 August 2009. After the ban on TEL, blood lead levels in U.S. children dramatically decreased. Researchers including Amherst College economist Jessica Wolpaw Reyes, Department of Housing and Urban Development
The United States Department of Housing and Urban Development (HUD) is one of the executive departments of the U.S. federal government. It administers federal housing and urban development laws. It is headed by the Secretary of Housing and U ...
consultant Rick Nevin, and Howard Mielke of Tulane University
Tulane University, officially the Tulane University of Louisiana, is a private research university in New Orleans, Louisiana. Founded as the Medical College of Louisiana in 1834 by seven young medical doctors, it turned into a comprehensive pu ...
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.
See also
* Elmer Keiser Bolton
Elmer Keiser Bolton (June 23, 1886 – July 30, 1968) was an American chemist and research director for DuPont, notable for his role in developing neoprene and directing the research that led to the discovery of nylon.
Personal life
Bolton wa ...
* Lead abatement
* List of petrol additives
References
Further reading
*
External links
Media articles
The Man Who Warned the World About Lead
(PBS / NOVA)
The Most Important Scientist You’ve Never Heard Of
BY Lucas Reilly, May 17, 2017, mentalfloss.com
The World Has Finally Stopped Using Leaded Gasoline. Algeria Used The Last Stockpile
August 30, 2021, Heard on All Things Considered, Camila Domonoske, NPR.
Official documents
*U.S. Gov't, National Institute for Occupational Safety and Health
Scientific papers and journal articles
*Kovarik, Bill (1999)
* ttps://www.aopa.org/advocacy/advocacy-briefs/regulatory-brief-avgas-100ll-alternatives True unleaded alternative for 100LL needed for general aviation*Jamie Lincoln Kitman:
The Secret History of Lead
'. In: The Nation, 2 March 2000.
{{Authority control
Organolead compounds
Antiknock agents