Fuels

The most common distillations of petroleum are fuels. Fuels include:

Ethane and other short-chain alkanes Diesel fuel (petrodiesel) Fuel oils Gasoline Jet fuel Kerosene Liquefied petroleum gas (LPG) Natural gas

Ethane is a chemical compound with chemical formula C2H6. It is the only two-carbon alkane, that is, an aliphatic hydrocarbon. At standard temperature and pressure, ethane is a colorless, odorless gas. Ethane is isolated on an industrial scale from natural gas, and as a byproduct of petroleum refining. Its chief use is as petrochemical feedstock for ethylene production.

Chemistry
In the laboratory, ethane may be conveniently prepared by Kolbe electrolysis. In this technique, an aqueous solution of an acetate salt is electrolysed. At the anode, acetate is oxidized to produce carbon dioxide and methyl radicals, and the highly reactive methyl radicals combine to produce ethane: CH3COO CH3 + CO2 + e CH3 + CH3 C2H6 Another method, the oxidation of acetic anhydride by peroxides, is conceptually similar. The chemistry of ethane also involves chiefly free radical reactions. Ethane can react with the halogens, especially chlorine and bromine, by free radical halogenation. This reaction proceeds through the propagation of the ethyl radical: C2H5 + Cl2 C2H5Cl + Cl Cl + C2H6 C2H5 + HCl Because halogenated ethanes can undergo further free radical halogenation, this process results in a mixture of several halogenated products. In the chemical industry, more selective chemical reactions are used for the production of any particular two-carbon halocarbon.

Combustion
The complete combustion of ethane releases 1561 kJ/mol, or 51.9 kJ/g, of heat, and produces carbon dioxide and water according to the chemical equation 2 C2H6 + 7 O2 4 CO2 + 6 H2O + 3122 kJ/mol Combustion occurs by a complex series of free-radical reactions. Computer simulations of the chemical kinetics of ethane combustion have included hundreds of reactions. An important series of reaction in ethane combustion is the combination of an ethyl radical with oxygen, and the subsequent breakup of the resulting peroxide into ethoxy and hydroxyl radicals. C2H5 + O2 C2H5OO C2H5OO + HR C2H5OOH + R C2H5OOH C2H5O + OH The principal carbon-containing products of incomplete ethane combustion are singlecarbon compounds such as carbon monoxide and formaldehyde. One important route by which the carbon-carbon bond in ethane is broken to yield these single-carbon products is the decomposition of the ethoxy radical into a methyl radical and formaldehyde, which can in turn undergo further oxidation. C2H5O CH3 + CH2O Some minor products in the incomplete combustion of ethane include acetaldehyde, methane, methanol, and ethanol. At higher temperatures, especially in the range 600900 C, ethylene is a significant product. It arises via reactions like C2H5 + O2 C2H4 + OOH Similar reactions (although with species other than oxygen as the hydrogen abstractor) are involved in the production of ethylene from ethane in steam cracking.

Production
After methane, ethane is the second-largest component of natural gas. Natural gas from different gas fields varies in ethane content from less than 1% to over 6% by volume. Prior to the 1960s, ethane and larger molecules were typically not separated from the methane component of natural gas, but simply burnt along with the methane as a fuel. Today, however, ethane is an important petrochemical feedstock, and it is separated from the other components of natural gas in most well-developed gas fields. Ethane can also be separated from petroleum gas, a mixture of gaseous hydrocarbons that arises as a byproduct of petroleum refining. Economics of building and running processing plants can change, however. If the relative value of sending the unprocessed natural gas to a consumer

exceeds the value of extracting ethane, then the plant may not be run. This can cause operational issues managing the changing quality of the gas in downstream systems.[1] Ethane is most efficiently separated from methane by liquefying it at cryogenic temperatures. Various refrigeration strategies exist: the most economical process presently in wide use employs turboexpansion, and can recover over 90% of the ethane in natural gas. In this process, chilled gas expands through a turbine; as it expands, its temperature drops to about -100 C. At this low temperature, gaseous methane can be separated from the liquefied ethane and heavier hydrocarbons by distillation. Further distillation then separates ethane from the propane and heavier hydrocarbons.

Uses
The chief use of ethane is in the chemical industry (usually uses a catalyst to boost up the reaction), in the production of ethylene by steam cracking. When diluted with steam and briefly heated to very high temperatures (900 C or more), heavy hydrocarbons break down into lighter hydrocarbons, and saturated hydrocarbons become unsaturated. Ethane is favored for ethylene production because the steam cracking of ethane is fairly selective for ethylene, while the steam cracking of heavier hydrocarbons yields a product mixture poorer in ethylene, and richer in heavier olefins such as propylene and butadiene, and in aromatic hydrocarbons. Experimentally, ethane is under investigation as a feedstock for other commodity chemicals. Oxidative chlorination of ethane has long appeared to be a potentially more economical route to vinyl chloride than ethylene chlorination. Many processes for carrying out this reaction have been patented, but poor selectivity for vinyl chloride and corrosive reaction conditions (specifically, a hydrochloric acid-containing reaction mixture at temperatures greater than 500 C) have discouraged the commercialization of most of them. Presently, INEOS operates a 1000 t/a ethane-to-vinyl chloride pilot plant at Wilhelmshaven in Germany. Similarly, the Saudi Arabian firm SABIC has announced construction of a 30,000 t/a plant to produce acetic acid by ethane oxidation at Yanbu. This economic viability of this process may rely on the low cost of ethane near Saudi oil fields, and it may not be competitive with methanol carbonylation elsewhere in the world. Ethane can be used as a refrigerant in cryogenic refrigeration systems. On a much smaller scale, in scientific research, liquid ethane is used to vitrify water-rich samples for electron microscopy. A thin film of water, quickly immersed in liquid ethane at -150 C or colder, freezes too quickly for water to crystallize. This rapid freezing does not disrupt the structure of soft objects present in the liquid state, as the formation of ice crystals can do. Ethane occurs as a trace gas in the Earth's atmosphere, having a concentration at sea level of around 0.5 ppbv[1] at present, though its pre-industrial concentration is likely to have been substantially less as a large proportion of the ethane in today's atmosphere probably originated as unburned fossil fuels. Although ethane is a greenhouse gas, it is much less

abundant than methane and also less efficient relative to mass. It has also been detected as a trace component in the atmospheres of all four giant planets, and in the atmosphere of Saturn's moon Titan. Atmospheric ethane results from the Sun's photochemical action on methane gas, also present in these atmospheres: ultraviolet photons of shorter wavelengths than 160 nm can photo-dissociate the methane molecule into a methyl radical and a hydrogen atom. When two methyl radicals recombine, the result is ethane: CH4 CH3 + H CH3 + CH3 C2H6 In the case of Titan, it was once widely hypothesized that ethane produced in this fashion rained back onto the moon's surface, and over time had accumulated into hydrocarbon seas or oceans covering much of the moon's surface. Infrared telescopic observations cast significant doubt on this hypothesis, and the Huygens probe, which landed on Titan in 2005, failed to observe any surface liquids, although it did photograph features that could be presently dry drainage channels. In December 2007 the Cassini probe found at least one lake at Titan's south pole, now called Ontario Lacus because of the lake's similar area to Lake Ontario on Earth (approximately 20,000 km). Further analysis of infrared spectroscopic data presented in July 2008[2] provided stronger evidence for the presence of liquid ethane in Ontario Lacus. In 1996, ethane was detected in Comet Hyakutake, and it has since been detected in some other comets. The existence of ethane in these distant solar system bodies may implicate ethane as a primordial component of the solar nebula from which the sun and planets are believed to have formed.

Diesel
Diesel or diesel fuel (IPA: /dizl/) in general is any fuel used in diesel engines. The most common is a specific fractional distillate of petroleum fuel oil, but alternatives that are not derived from petroleum, such as biodiesel, biomass to liquid (BTL) or gas to liquid (GTL) diesel, are increasingly being developed and adopted. To distinguish these types, petroleum-derived diesel is increasingly called petrodiesel.[citation needed] Ultra-low sulfur diesel (ULSD) is a term used to describe a standard for defining diesel fuel with substantially lowered sulfur contents. As of 2007, almost every diesel fuel available in America and Europe is the ULSD type.

Burning efficiency

The density of petroleum diesel is about 0.85 kg/l (7.09 lbs/gallon) whereas petrol (gasoline) has a density of about 0.72 kg/l (6.01 lbs/gallon), about 15% less. When burnt, diesel typically releases about 38.6 MJ/l (138,700 Btu per US gallon), whereas gasoline releases 34.9 MJ/l (125,000 Btu per US gallon), about 11% less.[2] Diesel is generally simpler to refine from petroleum than gasoline. The price of diesel traditionally rises during colder months as demand for heating oil rises, which is refined in much the same way. Due to its higher level of pollutants, diesel must undergo additional filtration[citation needed] which contributes to a sometimes higher cost. In many parts of the United States and throughout the UK and Australia[3] diesel may be higher priced than petrol.[4] Reasons for higher priced diesel include the shutdown of some refineries in the Gulf of Mexico, diversion of mass refining capacity to gasoline production, and a recent transfer to ultra-low sulfur diesel (ULSD), which causes infrastructural complications.[5]

Use as vehicle fuel

Unlike Petroleum ether and Liquefied petroleum gas engines, diesel engines do not use high voltage spark ignition (sparkplugs). A engine running on diesel compresses the air inside the cylinder to high pressures and temperatures (compression ratios from 15:1 to 25:1 are common); the diesel is generally injected directly into the cylinder near the end of the compression stroke. The high temperatures inside the cylinder causes the diesel fuel to react with the air oxygen (to burn), heating and expanding the burning mixture in order to convert the thermal/pressure difference into mechanical work, i.e. to move the piston (glow plugs are used to assist starting the engine to pre-warm cylinders to reach a minimum operating temperature). The high compression ratios and throttle-less operation of the diesels generally result in diesel engines being more efficient than many spark-ignited engines. This and being less flammable/explosive than gasoline are the main reasons for military use of diesel in armoured fighting vehicles like tanks and humvees. Engines running on diesel also provide more torque and are less likely to stall; as they run at a lower RPM, they will rather stutter a lot before stalling.[citation needed] An important disadvantage of diesel as a vehicle fuel, compared to gasoline or other petroleum derived fuels, is that its viscosity increases quickly as the fuel's temperature decreases, turning into a non-flowing gel at temperatures as high as -19 C (-2.2 F) or -15 C (+5 F), which can't be pumped by regular fuel pumps. Special low temperature diesel contains additives that keep it in a more liquid state at lower temperatures, yet starting a diesel engine in very cold weather still poses considerable difficulties.

Use as car fuel

Diesel-powered cars generally have a better fuel economy than equivalent gasoline engines and produce less greenhouse gas emission. Their greater economy is due to the higher energy per-litre content of diesel fuel and the intrinsic efficiency of the diesel engine. While petrodiesel's 15% higher density results in 15% higher greenhouse gas emissions per litre compared to gasoline,[6] the 2040% better fuel economy achieved by modern diesel-

engined automobiles offsets the higher-per-liter emissions of greenhouse gases, and produces 10-20 percent less GHG emissions than comparable gasoline vehicles.[7][8][9] However, the EPA carbon footprint estimates do not include the carbon cost of vehicle manufacture, nor the carbon cost of filtering particulates, sulfates, and nitrates emissions. Biodiesel-powered diesel engines offer substantially improved emission reductions compared to petro-diesel or gasoline-powered engines, while retaining most of the fuel economy advantages over conventional gasoline-powered automobiles.

Reduction of sulfur emissions

In the past, diesel fuel contained higher quantities of sulfur. European emission standards and preferential taxation have forced oil refineries to dramatically reduce the level of sulfur in diesel fuels. In the United States, more stringent emission standards have been adopted with the transition to ULSD starting in 2006 and becoming mandatory on June 1, 2010 (see also diesel exhaust). U.S. diesel fuel typically also has a lower cetane number (a measure of ignition quality) than European diesel, resulting in worse cold weather performance and some increase in emissions.[10] This is one reason why U.S. drivers of large trucks have increasingly turned to biodiesel fuels with their generally higher cetane ratings.

Environment hazards of sulfur

High levels of sulfur in diesel are harmful for the environment because they prevent the use of catalytic diesel particulate filters to control diesel particulate emissions, as well as more advanced technologies, such as nitrogen oxide (NOx) adsorbers (still under development), to reduce emissions. However, the process for lowering sulfur also reduces the lubricity of the fuel, meaning that additives must be put into the fuel to help lubricate engines. Biodiesel and biodiesel/petrodiesel blends, with their higher lubricity levels, are increasingly being utilized as an alternative. The U.S. annual consumption of diesel fuel in 2006 was about 190 billion litres (42 billion imperial gallons or 50 billion US gallons). [1]

Synthetic diesel
Wood, hemp, straw, corn, garbage, food scraps, and sewage-sludge may be dried and gasified to synthesis gas. After purification the Fischer-Tropsch process is used to produce synthetic diesel.[12] This means that synthetic diesel oil may be one route to biomass based diesel oil. Such processes are often called Biomass-To-Liquids or BTL. Synthetic diesel may also be produced out of natural gas in the Gas-to-liquid (GTL) process or out of coal in the Coal-to-liquid (CTL) process. Such synthetic diesel has 30% less particulate emissions than conventional diesel (US- California).[13]

Biodiesel
Biodiesel can be obtained from vegetable oil (vegidiesel/vegifuel), or animal fats (biolipids), using transesterification. Biodiesel is a non-fossil fuel alternative to petrodiesel. It can also be mixed with petrodiesel in any amount in modern engines.[citation needed] Biodiesel

has a higher gel point than petrodiesel, but is comparable to diesel. This can be overcome by using a biodiesel/petrodiesel blend, or by installing a fuel heater, but this is only necessary during the colder months. A diesel-biodiesel mix results in lower emissions than either can achieve alone,[14] except for NOx emissions. A small fraction of biodiesel can be used as an additive in low-sulfur formulations of diesel to increase the lubricity lost when the sulfur is removed. In the event of fuel spills, biodiesel is easily washed away with ordinary water and is nontoxic compared to other fuels. Biodiesel can be produced using kits. Certain kits allow for processing of used vegetable oil that can be run through any conventional diesel motor with modifications. The modification needed is the replacement of fuel lines from the intake and motor and all affected rubber fittings in injection and feeding pumps a.s.o. This is because biodiesel is an effective solvent and will replace softeners within unsuitable rubber with itself over time. Synthetic gaskets for fittings and hoses prevent this. Chemically, most biodiesel consists of alkyl (usually methyl) esters instead of the alkanes and aromatic hydrocarbons of petroleum derived diesel. However, biodiesel has combustion properties very similar to petrodiesel, including combustion energy and cetane ratings. Paraffin biodiesel also exists. Due to the purity of the source, it has a higher quality than petrodiesel.

Biodiesel emissions
The use of biodiesel blended diesel fuels in fractions up to 99% result in substantial emission reductions. Sulfur oxide and sulfate emissions, major components of acid rain, are essentially eliminated with pure biodiesel and substantially reduced using biodiesel blends with minor quantities of ULSD petrodiesel. Use of biodiesel also results in substantial reductions of unburned hydrocarbons, carbon monoxide, and particulate matter compared to either gasoline or petrodiesel. C02, or carbon monoxide emissions using biodiesel are substantially reduced, on the order of 50% compared to most petrodiesel fuels. The exhaust emissions of particulate matter from biodiesel have been found to be 30 percent lower than overall particulate matter emissions from petrodiesel. The exhaust emissions of total hydrocarbons (a contributing factor in the localized formation of smog and ozone) are up to 93 percent lower for biodiesel than diesel fuel. Biodiesel emissions of nitrogen oxides can sometimes increase slightly. However, biodiesel's complete lack of sulfur and sulfate emissions allows the use of NOx control technologies, such as AdBlue, that cannot be used with conventional diesel, allowing the management and control of nitrous oxide emissions. Biodiesel also may reduce health risks associated with petroleum diesel. Biodiesel emissions showed decreased levels of PAH and nitrited PAH compounds which have been identified as potential cancer causing compounds. In recent testing, PAH compounds were reduced by 75 to 85 percent, with the exception of benzo(a)anthracene, which was reduced by roughly 50 percent. Targeted nPAH compounds were also reduced dramatically with biodiesel fuel, with 2-nitrofluorene and 1-nitropyrene reduced by 90 percent, and the rest of the nPAH compounds reduced to only trace levels.[15]

Fuel oil is a fraction obtained from petroleum distillation, either as a distillate or a residue. Broadly speaking, fuel oil is any liquid petroleum product that is burned in a furnace or boiler for the generation of heat or used in an engine for the generation of power, except oils having a flash point of approximately 40 (104 ) and oils burned in cotton or wool-wick burners. In this sense, diesel is a type of fuel oil. Fuel oil is made of long hydrocarbon chains, particularly alkanes, cycloalkanes and aromatics. The term fuel oil is also used in a stricter sense to refer only to the heaviest commercial fuel that can be obtained from crude oil, heavier than gasoline and naphtha.

Six classes
Fuel oil in the United States is classified into six classes, numbered 1 through 6, according to its boiling point, composition and purpose. The boiling point, ranging from 175 to 600 C, and carbon chain length, 20 to 70 atoms, of the fuel increases with fuel oil number. Viscosity also increases with number, and the heaviest oil has to be heated to get it to flow. Price usually decreases as the fuel number increases. No. 1 fuel oil, No. 2 fuel oil and No. 3 fuel oil are variously referred to as distillate fuel oils, diesel fuel oils, light fuel oils, gasoil or just distillate. For example, No. 2 fuel oil, No. 2 distillate and No. 2 diesel fuel oil are almost the same thing (diesel is different in that it also has a cetane number limit which describes the ignition quality of the fuel). Distillate fuel oils are distilled from crude oil. Gas oil refers to the process of distillation. The oil is heated, becomes a gas and then condenses. It differentiates distillates from residual oil (RFO). No. 1 is similar to kerosene and is the fraction that boils off right after gasoline. No. 2 is the diesel that trucks and some cars run on, leading to the name "road diesel". It is the same thing as heating oil. No. 3 is a distillate fuel oil and is rarely used. No. 4 fuel oil is usually a blend of distillate and residual fuel oils, such as No. 2 and 6; however, sometimes it is just a heavy distillate. No. 4 may be classified as diesel, distillate or residual fuel oil. No. 5 fuel oil and No. 6 fuel oil are called residual fuel oils (RFO) or heavy fuel oils. As far more No. 6 than No. 5 is produced, the terms heavy fuel oil and residual fuel oil are sometimes used as synonyms for No. 6. They are what remains of the crude oil after gasoline and the distillate fuel oils are extracted through distillation. No. 5 fuel oil is a mixture of No. 6 (about 75-80%) with No. 2. No. 6 may also contain a small amount of No. 2 to get it to meet specifications. Residual fuel oils are sometimes called light when they have been mixed with distillate fuel oil, while distillate fuel oils are called heavy when they have been mixed with residual fuel oil. Heavy gas oil, for example, is a distillate that contains residual fuel oil. The ready availability of very heavy grades of fuel oil is often due to the success of catalytic cracking of fuel to release more valuable fractions and leave heavy residue. The US nomenclature is used in most of the world. In the United Kingdom the classes comprise 6 commonly used fuels using alphabetical designations, from Class C1 (kerosene)

to Class G (heavy fuel oil). There is a Class H designation which is not yet in general use. The characteristics of these oils are specified in British Standard BS2869:1998 - soon to be updated to BS2869:2006.

Bunker fuel
Bunker fuel is technically any type of fuel oil used aboard ships. It gets its name from the containers on ships and in ports that it is stored in; in the days of steam they were coal bunkers but now they are bunker-fuel tanks. The Australian Customs and the Australian Tax Office defines a bunker fuel as the fuel that powers the engine of a ship or aircraft. Bunker A is No. 2 fuel oil, bunker B is No. 4 or No. 5 and bunker C is No. 6. Since No. 6 is the most common, "bunker fuel" is often used as a synonym for No. 6. No. 5 fuel oil is also called navy special fuel oil or just navy special, No. 6 or 5 are also called furnace fuel oil (FFO); the high viscosity requires heating, usually by a reticulated low pressure steam system, before the oil can be pumped from a bunker tank. In the context of shipping, the labelling of bunkers as previously described is rarely used in modern practice. Table of fuel oils Name No. 1 fuel oil No. 2 fuel oil No. 3 fuel oil No. 4 fuel oil No. 5 fuel oil No. 6 fuel oil

Alias No. 1 distillate No. 2 distillate No. 3 distillate No. 4 distillate No. 5 residual fuel oil No. 6 residual fuel oil

Alias No. 1 diesel fuel No. 2 diesel fuel No. 3 diesel fuel No. 4 residual fuel oil Heavy fuel oil Heavy fuel oil

Type Distillate Distillate Distillate

Chain Length 9-16 10-20

Distillate/Residual 12-70 Residual Residual 12-70 20-70

, with a moderate octane rating, high olefins (alkene) content, and moderate aromatics level. Here, "cat" is short for "catalytic". Hydrocrackate (Heavy, Mid, and Light), produced from a hydrocracker, with medium to low octane rating and moderate aromatic levels. Virgin or Straight-run Naphtha (has many names), directly from crude oil with low octane rating, low aromatics (depending on the crude oil), some naphthenes (cycloalkanes) and no olefins (alkenes). Alkylate, produced in an alkylation unit, with a high octane rating and which is pure paraffin (alkane), mainly branched chains. Isomerate (various names) which is obtained by isomerising the pentane and hexane in light virgin naphthas to yield their higher octane isomers.

(The terms used here are not always the correct chemical terms. They are the jargon normally used in the oil industry. The exact terminology for these streams varies by refinery and by country.) Overall a typical gasoline is predominantly a mixture of paraffins (alkanes), naphthenes (cycloalkanes), and olefins (alkenes). The exact ratios can depend on

the oil refinery that makes the gasoline, as not all refineries have the same set of processing units. the crude oil feed used by the refinery. the grade of gasoline, in particular the octane rating.

Currently many countries set tight limits on gasoline aromatics in general, benzene in particular, and olefin (alkene) content. This is increasing the demand for high octane pure paraffin (alkane) components, such as alkylate, and is forcing refineries to add processing units to reduce the benzene content. Gasoline can also contain some other organic compounds: such as organic ethers (deliberately added), plus small levels of contaminants, in particular sulfur compounds such as disulfides and thiophenes. Some contaminants, in particular thiols and hydrogen sulfide, must be removed because they cause corrosion in engines. Sulfur compounds are usually removed by hydrotreating, yielding hydrogen sulfide which can then be transformed into elemental sulfur via the Claus process. The density of gasoline is 0.710.77 g/cm3,[8] (in English units, approx. .026 lb/in3 or 6.073 lb/gal) which means it floats on water. This may be advantageous in the event of a spill. It is flammable and can burn while floating over water.

Volatility
Gasoline is more volatile than diesel oil, Jet-A or kerosene, not only because of the base constituents, but because of the additives that are put into it. The final control of volatility is often achieved by blending with butane. The Reid Vapor Pressure test is used to measure the volatility of gasoline. The desired volatility depends on the ambient temperature: in hotter climates, gasoline components of higher molecular weight and thus lower volatility are used. In cold climates, too little volatility results in cars failing to start. In hot climates, excessive volatility results in what is known as "vapour lock" where combustion fails to occur, because the liquid fuel has changed to a gaseous fuel in the fuel lines, rendering the fuel pump ineffective and starving the engine of fuel. In the United States, volatility is regulated in large urban centers to reduce the emission of unburned hydrocarbons. In large cities, so-called reformulated gasoline that is less prone to evaporation, among other properties, is required. In Australia summer petrol volatility limits are set by State Governments and vary between capital cities. Most countries simply have a summer, winter and perhaps intermediate limit.

Volatility standards may be relaxed (allowing more gasoline components into the atmosphere) during emergency anticipated gasoline shortages. For example, on 31 August 2005 in response to Hurricane Katrina, the United States permitted the sale of nonreformulated gasoline in some urban areas, which effectively permitted an early switch from summer to winter-grade gasoline. As mandated by EPA administrator Stephen L. Johnson, this "fuel waiver" was made effective through 15 September 2005.[9] Though relaxed volatility standards may increase the atmospheric concentration of volatile organic compounds in warm weather, higher volatility gasoline effectively increases a nation's gasoline supply because the amount of butane in the gasoline pool is allowed to increase.
[citation needed]

Octane rating
An important characteristic of gasoline is its octane rating, which is a measure of how resistant gasoline is to the abnormal combustion phenomenon known as detonation (also known as knocking, pinging, spark knock, and other names). Deflagration is the normal type of combustion. Octane rating is measured relative to a mixture of 2,2,4trimethylpentane (an isomer of octane) and n-heptane. There are a number of different conventions for expressing the octane rating; therefore, the same fuel may be labeled with a different number, depending upon the system used. The octane rating became important in the search for higher output powers from aero engines in the late 1930's and the 1940's as it allowed higher compression ratios to be used.

Additives
Lead
The mixture known as gasoline, when used in high compression internal combustion engines, has a tendency to autoignite(detonation) causing a damaging "engine knocking" (also called "pinging") noise. Early research into this effect was led by A.H. Gibson and Harry Ricardo in England and Thomas Midgley and Thomas Boyd in the United States. The discovery that lead additives modified this behavior led to the widespread adoption of the practice in the 1920s and therefore more powerful higher compression engines. The most popular additive was tetra-ethyl lead. However, with the discovery of the environmental and health damage caused by the lead, and the incompatibility of lead with catalytic converters found on virtually all newly sold US automobiles since 1975, this practice began to wane (encouraged by many governments introducing differential tax rates) in the 1980s. Most countries are phasing out leaded fuel; different additives have replaced the lead compounds. The most popular additives include aromatic hydrocarbons, ethers and alcohol (usually ethanol or methanol). In the US, where lead had been blended with gasoline (primarily to boost octane levels) since the early 1920s, standards to phase out leaded gasoline were first implemented in 1973. In 1995, leaded fuel accounted for only 0.6% of total gasoline sales and less than 2,000 short tons of lead per year. From January 1, 1996, the Clean Air Act banned the sale

of leaded fuel for use in on-road vehicles. Possession and use of leaded gasoline in a regular on-road vehicle now carries a maximum $10,000 fine in the US. However, fuel containing lead may continue to be sold for off-road uses, including aircraft, racing cars, farm equipment, and marine engines.[15] The ban on leaded gasoline led to thousands of tons of lead not being released in the air by automobiles. Similar bans in other countries have resulted in lowering levels of lead in people's bloodstreams.[16][17] A side effect of the lead additives was protection of the valve seats from erosion. Many classic cars' engines have needed modification to use lead-free fuels since leaded fuels became unavailable. However, "Lead substitute" products are also produced and can sometimes be found at auto parts stores. These were scientifically tested and some were approved by the Federation of British Historic Vehicle Clubs at the UK's Motor Industry Research Association (MIRA) in 1999. http://www.fbhvc.co.uk/fuel/index.htm Gasoline, as delivered at the pump, also contains additives to reduce internal engine carbon buildups, improve combustion, and to allow easier starting in cold climates. In some parts of South America, Asia, Eastern Europe and the Middle East, leaded gasoline is still in use. Leaded gasoline was phased out in sub-Saharan Africa effective 1 January 2006. A growing number of countries have drawn up plans to ban leaded gasoline in the near future.

MMT
Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used for many years in Canada and recently in Australia to boost octane. It also helps old cars designed for leaded fuel run on unleaded fuel without need for additives to prevent valve problems. US Federal sources state that MMT is suspected to be a powerful neurotoxin and respiratory toxin,[18] and a large Canadian study concluded that MMT impairs the effectiveness of automobile emission controls and increases pollution from motor vehicles.
[19]

In 1977 use of MMT was banned in the US by the Clean Air Act until the Ethyl Corporation could prove that the additive would not lead to failure of new car emissionscontrol systems. As a result of this ruling, the Ethyl Corporation began a legal battle with the EPA, presenting evidence that MMT was harmless to automobile emissions-control systems. In 1995 the US Court of Appeals ruled that the EPA had exceeded its authority, and MMT became a legal fuel additive in the US. MMT is nowadays manufactured by the Afton Chemical Corporation division of Newmarket Corporation.[20]

Ethanol
In the United States, ethanol is sometimes added to gasoline but sold without an indication that it is a component. Chevron, 76, Shell, and several other brands market ethanolgasoline blends.[citation needed]

In several states, ethanol is added by law to a minimum level which is currently 5.9%. Most fuel pumps display a sticker stating that the fuel may contain up to 10% ethanol, an intentional disparity which allows the minimum level to be raised over time without requiring modification of the literature/labeling. The bill which was being debated at the time the disclosure of the presence of ethanol in the fuel was mandated has recently passed. This law (Energy Policy Act of 2005) will require all auto fuel to contain at least 10% ethanol. Many call this fuel mix gasohol. In the EU, 5% ethanol can be added within the common gasoline spec (EN 228). Discussions are ongoing to allow 10% blending of ethanol. Most countries (fuel distributors) today do not add so much ethanol.[citation needed] Most gasoline (petrol) sold in Sweden has 5% ethanol added. In Brazil, the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) requires that gasoline for automobile use has 23% of ethanol added to its composition.

Dye
In the United States the most commonly used aircraft gasoline, avgas, or aviation gas, is known as 100LL (100 octane, low lead) and is dyed blue. Red dye has been used for identifying untaxed (non-highway use) agricultural diesel. The UK uses red dye to differentiate between regular diesel fuel, (often referred to as DERV from Diesel-Engined Road Vehicle), which is undyed, and diesel intended for agricultural and construction vehicles like excavators and bulldozers. Red diesel is still occasionally used on HGVs which use a separate engine to power a loader crane. This is a declining practice however, as many loader cranes are powered directly by the tractor unit.

Oxygenate blending
Oxygenate blending adds oxygen to the fuel in oxygen-bearing compounds such as MTBE, ETBE and ethanol, and so reduces the amount of carbon monoxide and unburned fuel in the exhaust gas, thus reducing smog. In many areas throughout the US oxygenate blending is mandated by EPA regulations to reduce smog and other airborne polutants. For example, in Southern California, fuel must contain 2% oxygen by weight, resulting in a mixture of 5.6% ethanol in gasoline. The resulting fuel is often known as reformulated gasoline (RFG) or oxygenated gasoline. The federal requirement that RFG contain oxygen was dropped May 6, 2006 because the industry had developed VOC-controlled RFG that did not need additional oxygen.[21] MTBE use is being phased out in some states due to issues with contamination of ground water. In some places, such as California, it is already banned. Ethanol and to a lesser extent the ethanol derived ETBE are a common replacements. Especially since ethanol derived from biomatter such as corn, sugar cane or grain is frequent, this will often be referred to as bio-ethanol. A common ethanol-gasoline mix of 10% ethanol mixed with gasoline is called gasohol or E10, and an ethanol-gasoline mix of 85% ethanol mixed with gasoline is called E85. The most extensive use of ethanol takes place in Brazil, where the

ethanol is derived from sugarcane. In 2004, over 3,400 million US gallons (13 million m) of ethanol was produced in the United States for fuel use, mostly from corn, and E85 is slowly becoming available in much of the United States. Unfortunately many of the relatively few stations vending E85 are not open to the general public.[22] The use of bioethanol, either directly or indirectly by conversion of such ethanol to bio-ETBE, is encouraged by the European Union Directive on the Promotion of the use of biofuels and other renewable fuels for transport. However since producing bio-ethanol from fermented sugars and starches involves distillation, ordinary people in much of Europe cannot legally ferment and distill their own bio-ethanol at present (unlike in the US where getting a BATF distillation permit has been easy since the 1973 oil crisis.)