gasoline

"Petrol" redirects here. For other uses, see Petrol (disambiguation). For the bird group, see petrel.

A jar containing gasoline

Gasoline  /ˈɡæsəliːn/, or petrol  /ˈpɛtrəl/, is a transparent petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasolines also contain ethanol as an alternative fuel. In North America, the term "gasoline" is often shortened in colloquial usage to "gas", whereas most current or former Commonwealth nations use the term "petrol". Under normal ambient conditions its material state is liquid, unlike liquefied petroleum gas or "natural gas".

Properties

Volatility

Gasoline is more volatile than diesel oil, Jet-A, or kerosene, not only because of the base constituents, but also because of additives. Volatility is often controlled by blending with butane, which boils at -0.5 °C. The volatility of petrol is determined by the Reid vapor pressure (RVP) test. The desired volatility depends on the ambient temperature. In hot weather, petrol components of higher molecular weight and thus lower volatility are used. In cold weather, too little volatility results in cars failing to start.

In hot weather, excessive volatility results in what is known as "vapor 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. This effect mainly applies to camshaft-driven (engine mounted) fuel pumps which lack a fuel return line. Vehicles with fuel injection require the fuel to be pressurized, to within a set range. Because camshaft speed is nearly zero before the engine is started, an electric pump is used. It is located in the fuel tank so the fuel may also cool the high-pressure pump. Pressure regulation is achieved by returning unused fuel to the tank. Therefore, vapor lock is almost never a problem in a vehicle with fuel injection.

In the United States, volatility is regulated in large cities to reduce the emission of unburned hydrocarbons by the use of so-called reformulated gasoline that is less prone to evaporation. In Australia, summer petrol volatility limits are set by state governments and vary among states. Most countries simply have a summer, winter, and perhaps intermediate limit.

Volatility standards may be relaxed (allowing more gasoline components into the atmosphere) during 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, effectively permitting an early switch from summer to winter-grade gasoline. As mandated by EPA administrator Stephen L. Johnson, this "fuel waiver" was made effective until 15 September 2005.^[1]

Modern automobiles are also equipped with an evaporative emissions control system (called an EVAP system in automotive jargon), which collects evaporated fuel from the fuel tank in a charcoal-filled canister while the engine is stopped, and then releases the collected vapors into the engine intake for burning when the engine is running (usually only after it has reached normal operating temperature). The evaporative emissions control system also includes a sealed gas cap to prevent vapors from escaping via the fuel filler tube. Modern vehicles with OBD-II emissions control systems will illuminate the malfunction indicator light (MIL), "check engine" or “Service Engine Soon” light if the leak detection pump (LDP) detects a leak in the EVAP system. If the electronic control unit (ECU) or power-train control module (PCM) detects a leak, it will store an OBD-II code representing either a small or large leak, thus illuminating the MIL to indicate a failure. Some vehicles can detect whether the gas cap is incorrectly fitted, and will indicate this by illuminating a gas cap symbol on the dash.^{[citation needed]}

Octane rating

Internal combustion engines are designed to burn gasoline in a controlled process called deflagration. But in some cases, gasoline can also combust abnormally by detonation, which wastes energy and can damage the engine. This phenomenon is often referred to as engine knocking. One way to reduce detonation is to increase the gasoline's resistance to autoignition, which is expressed by its octane rating.

Octane rating is measured relative to a mixture of 2,2,4-trimethylpentane (an isomer of octane) and n-heptane. There are different conventions for expressing octane ratings, so a fuel may have several different octane ratings based on the measure used. Research octane number (RON) for commercially-available gasoline varies by country. In Finland, Sweden, and Norway, 95 RON is the standard for regular unleaded petrol and 98 RON is also available as a more expensive option. In the UK, ordinary regular unleaded petrol is 91 RON (not commonly available), premium unleaded petrol is always 95 RON, and super unleaded is usually 97-98 RON. However, both Shell and BP produce fuel at 102 RON for cars with high-performance engines, and the supermarket chain Tesco began in 2006 to sell super unleaded petrol rated at 99 RON. In the US, octane ratings in unleaded fuels can vary between 86 and 87 AKI (91-92 RON) for regular, through 89-90 AKI (94-95 RON) for mid-grade (European premium), up to 90-94 AKI (95-99 RON) for premium (European super).

The octane rating became important as the military sought higher output for aircraft engines in the late 1930s and the 1940s. A higher octane rating allows a higher compression ratio, and thus higher temperatures and pressures, which translate to higher power output. Some scientists even predicted that a nation with a good supply of high octane gasoline would have the advantage in air power.^[2]

Stability

Good quality gasoline should be stable almost indefinitely if stored properly. Such storage should be in an airtight container, to prevent oxidation or water vapors mixing, and at a stable cool temperature, to reduce the chance of the container leaking. When gasoline is not stored correctly, gums and solids may accumulate resulting in "stale fuel". The presence of these degradation products in fuel tank, lines, and carburetor or fuel injection components, make it harder to start the engine. Upon the resumption of regular vehicle usage, though, the buildups should eventually be cleaned up by the flow of fresh petrol. Fuel stabilizers can be used to extend the life of the fuel that is not or cannot be stored properly. Fuel stabilizer is commonly used for small engines, such as lawnmower and tractor engines, to promote quicker and more reliable starting. Users have been advised to keep gasoline containers and tanks more than half full and properly capped to reduce air exposure, to avoid storage at high temperatures, to run an engine for ten minutes to circulate the stabilizer through all components prior to storage, and to run the engine at intervals to purge stale fuel from the carburetor.^[3]

Energy content (high and low heating value)

Energy is obtained from the combustion of gasoline, the conversion of a hydrocarbon to carbon dioxide and water. The combustion of octane follows this reaction:

2 C₈H₁₈ + 25 O₂ → 16 CO₂ + 18 H₂O

Gasoline contains about 35 MJ/L (9.7 kW·h/L, 132 MJ/US gal, 36.6 kWh/US gal) (higher heating value) or 13 kWh/kg. Gasoline blends differ, and therefore actual energy content varies according to the season to season and producer by up to 4% more or less than the average, according to the US EPA. On average, about 19.5 US gallons (16.2 imp gal; 74 L) of gasoline are available from a 42-US-gallon (35 imp gal; 160 L) barrel of crude oil (about 46% by volume), varying due to quality of crude and grade of gasoline. The remaining residue comes off as products ranging from tar to naptha.^[4]

A high octane rated fuel, such as liquefied petroleum gas (LPG), has a lower energy content than lower octane rated gasoline^{[citation needed]}, resulting in an overall lower power output at the regular compression ratio of an engine run at on gasoline. However, with an engine tuned to the use of LPG (i.e. via higher compression ratios, such as 12:1 instead of 8:1), this lower power output can be overcome. This is because higher-octane fuels allow for a higher compression ratio hence a higher cylinder temperature, which improves efficiency. Also, increased mechanical efficiency is created by a higher compression ratio through the concommitant higher expansion ratio on the power stroke, which is by far the greater effect. The higher expansion ratio extracts more work from the high-pressure gas created by the combustion process. The applicable formula is PV=nRT. An Atkinson cycle engine uses the timing of the valve events to produce the benefits of a high expansion ratio without the disadvantages, chiefly detonation, of a high compression ratio. A high expansion ratio is also one of the two key reasons for the efficiency of Diesel engines, along with the elimination of pumping losses due to throttling of the intake air flow. A high compression ratio can be viewed as a necessary evil to have a high expansion ratio.

The lower energy content (per litre) of LPG in comparison to gasoline is due mainly to its lower density. Energy content per kilogram is higher than for gasoline (higher hydrogen to carbon ratio).^{[citation needed]}

Density

The specific gravity (or relative density) of gasoline ranges from 0.71–0.77 (719.7 kg/m³ ; 0.026 lb/in³; 6.073 lb/US gal; 7.29 lb/imp gal), higher densities having a greater volume of aromatics.^[5] Gasoline floats on water; water cannot generally be used to extinguish a gasoline fire, unless used in a fine mist.

Chemical analysis and production

Refinery in Minatitlán, Mexico

A pumpjack in the United States

An oil rig in the Gulf of Mexico

Gasoline is produced in oil refineries. Material that is separated from crude oil via distillation, called virgin or straight-run gasoline, does not meet the required specifications for modern engines (in particular octane rating; see below), but will form part of the blend.

Some of the main components of gasoline: isooctane, butane, an aromatic compound, and the octane enhancer MTBE.

The bulk of a typical gasoline consists of hydrocarbons with between four and 12 carbon atoms per molecule (commonly referred to as C4-C12).^[3]

The various refinery streams blended to make gasoline have different characteristics. Some important streams are:

• straight-run gasoline is distilled directly from crude oil. Once the leading source of fuel, its low octane rating required lead additives. It is low in aromatics (depending on the grade of crude oil), containing some naphthenes (cycloalkanes) and no olefins. About 0-20% of gasoline is derived from this material, in part because the supply of this fraction is insufficient and its RON is too low.
• reformate, produced in a catalytic reformer with a high octane rating and high aromatic content, and very low olefins (alkenes). Most of the benzene, toluene, and xylene (the so-called BTX) are more valuable as chemical feedstocks and are thus removed to some extent.
• cat cracked gasoline or cat cracked naphtha, produced from a catalytic cracker, with a moderate octane rating, high olefins (alkene) content, and moderate aromatics level.
• hydrocrackate (heavy, mid, and light) produced from a hydrocracker, with medium to low octane rating and moderate aromatic levels.
• alkylate is produced in an alkylation unit, involving the addition of isobutane to alkenes giving branched chains but low aromatics.
• isomerate is obtained by isomerizing low octane straight run gasoline to iso-parafins (like isooctane).

The terms above are the jargon used in the oil industry but terminology varies.

Overall, a typical gasoline is predominantly a mixture of paraffins (alkanes), naphthenes (cycloalkanes), and olefins (alkenes). The actual ratio depends on:

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

Currently, many countries set limits on gasoline aromatics in general, benzene in particular, and olefin (alkene) content. Such regulations led to increasing preference for high octane pure paraffin (alkane) components, such as alkylate, and is forcing refineries to add processing units to reduce benzene content.

Gasoline can also contain other organic compounds, such as organic ethers (deliberately added), plus small levels of contaminants, in particular organosulfur compounds, but these are usually removed at the refinery.

Additives

Antiknock additives

A plastic container for storing gasoline used in Germany

Most countries have phased out leaded fuel. Different additives have replaced the lead compounds. The most popular additives include aromatic hydrocarbons, ethers and alcohol (usually ethanol or methanol).

Tetraethyl lead

Gasoline, when used in high-compression internal combustion engines, has a tendency to autoignite (detonate) causing damaging "engine knocking" (also called "pinging" or "pinking") 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 their use in the 1920s, and therefore more powerful, higher compression engines. The most popular additive was tetra-ethyl lead. With the discovery of the extent of environmental and health damage caused by the lead, however, 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.

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 - 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 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.^[6] Similar bans in other countries have resulted in lowering levels of lead in people's bloodstreams.^[7][8]

Gasolines are also treated with metal deactivators, which are compounds that sequester (deactivate) metal salts that otherwise accelerate the formation of gummy residues. The metal impurities might arise from the engine itself or as contaminants in the fuel.

Detergents

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. High levels of detergent can be found in Top Tier Detergent Gasolines. These gasolines exceed the U.S. EPA's minimum requirement for detergent content. The specification for Top Tier Detergent Gasolines was developed by four automakers: GM, Honda, Toyota and BMW. According to the bulletin, the minimal EPA requirement is not sufficient to keep engines clean.^[9] Typical detergents include alkylamines and alkyl phosphates at the level of 50-100 ppm.^[3]

Ethanol

European Union

In the EU, 5% ethanol can be added within the common gasoline spec (EN 228). Discussions are ongoing to allow 10% blending of ethanol (available in French gas stations). Most gasoline sold in Sweden has 5-15% ethanol added.

Brazil

In Brazil, the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) requires gasoline for automobile use to have from 18 to 25% of ethanol added to its composition.^[10]

Australia

Legislation requires retailers to label fuels containing ethanol on the dispenser, and limits ethanol use to 10% of gasoline in Australia. Such gasoline is commonly called E10 by major brands, and its price per litre is less than that of regular unleaded petrol. (Though its cost per kilometre is sometimes greater than regular unleaded petrol, notably following the 2010–2011 Queensland floods.)

United States

In most states, ethanol is added by law to a minimum level which is currently 5.9%. Most fuel pumps display a sticker stating 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/labelling. Until late 2010, fuels retailers were only authorized to sell fuel containing up to 10 percent ethanol (E10), and most vehicle warranties (except for flexible fuel vehicles) authorize fuels that contain no more than 10 percent ethanol.^[11] In parts of the United States, ethanol is sometimes added to gasoline without an indication that it is a component.

Dye

In Australia, petrol tends to be dyed a light shade of purple.

In India petrol is dyed red

In, South Africa, unleaded fuel is dyed green and lead-replacement fuel is dyed red.

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 that use a separate engine to power a loader crane. This practice is declining, however, as many loader cranes are powered directly by the tractor unit.

In the United States, the most commonly used aircraft gasoline, avgas (aviation gas, known as 100LL for 100 octane, low lead) and is dyed blue. In the United States, 80, 100, and 145 (although rare) octane avgas sometimes are dyed red, green, and purple respectively. Red dye has also been used for identifying untaxed (off highway use) agricultural diesel.

Oxygenate blending

Oxygenate blending adds oxygen-bearing compounds such as MTBE, ETBE and ethanol. The presence of these oxygenates reduces the amount of carbon monoxide and unburned fuel in the exhaust gas. In many areas throughout the US, oxygenate blending is mandated by EPA regulations to reduce smog and other airborne pollutants. 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, or in the case of California, California reformulated gasoline. The federal requirement that RFG contain oxygen was dropped on 6 May 2006 because the industry had developed VOC-controlled RFG that did not need additional oxygen.^[12]

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 common replacements. Since most ethanol is derived from biomass, such as corn, sugar cane or grain, it is referred to as bioethanol. 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 3.4 billion US gallons (2.8 billion imp gal/13 million m³) 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, though many of the relatively few stations vending E85 are not open to the general public.^[13] 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. Since producing bioethanol from fermented sugars and starches involves distillation, though, ordinary people in much of Europe cannot legally ferment and distill their own bioethanol at present (unlike in the US, where getting a BATF distillation permit has been easy since the 1973 oil crisis).

Safety

Environmental considerations

Combustion of one US gallon of gasoline produces about 19.4 pounds (8.8 kg) of carbon dioxide (converts to 2.33 kg/litre), a greenhouse gas.^[14]

The chief risks of such leaks come not from vehicles, but from gasoline delivery truck accidents and leaks from storage tanks. Because of this risk, most (underground) storage tanks now have extensive measures in place to detect and prevent any such leaks, such as sacrificial anodes.

The main concern with gasoline on the environment, aside from the complications of its extraction and refining, is the potential effect on the climate. Unburnt gasoline and evaporation from the tank, when in the atmosphere, react in sunlight to produce photochemical smog. Addition of ethanol increases the volatility of gasoline, potentially worsening the problem.

Toxicity

The material safety data sheet for unleaded gasoline shows at least 15 hazardous chemicals occurring in various amounts, including benzene (up to 5% by volume), toluene (up to 35% by volume), naphthalene (up to 1% by volume), trimethylbenzene (up to 7% by volume), methyl tert-butyl ether (MTBE) (up to 18% by volume, in some states) and about ten others.^[15] Hydrocarbons in gasoline generally exhibit low acute toxicities, with LD50 of 700 – 2700 mg/kg for simple aromatic compounds.^[16] Benzene and many antiknocking additives are carcinogenic.

Inhalation

Huffed gasoline is a common intoxicant that has become epidemic in some poorer communities and indigenous groups in Australia, Canada, New Zealand, some Pacific Islands, and the US.^[17] In response, Opal fuel has been developed by the BP Kwinana Refinery in Australia, and contains only 5% aromatics (unlike the usual 25%) which weakens the effects of inhalation.^[18]

Flammability

Uncontrolled burning of gasoline produces large quantities of soot.

Like other alkanes, gasoline burns in a limited range of its vapor phase and, coupled with its volatility, this makes leaks highly dangerous when sources of ignition are present. Gasoline has a lower explosion limit of 1.4% by volume and an upper explosion limit of 7.6%. If the concentration is below 1.4% the air-gasoline mixture is too lean and will not ignite. If the concentration is above 7.6% the mixture is too rich and also will not ignite. However, gasoline vapor rapidly mixes and spreads with air, making unconstrained gasoline quickly flammable. Many accidents involve gasoline being used in an attempt to light bonfires; rather than helping the material on the bonfire to burn, some of the gasoline vaporises quickly after being poured and mixes with the surrounding air, so when the fire is lit a moment later, the vapor surrounding the bonfire instantly ignites in a large fireball, engulfing the unwary user. The vapor is also heavier than air and tends to collect in garage inspection pits.

Usage and pricing

UK petrol prices

The US accounts for about 44% of the world’s gasoline consumption.^[19] In 2003 The US consumed 476.474 gigalitres (1.25871×10¹¹ US gal; 1.04810×10¹¹ imp gal),^[20] which equates to 1.3 gigalitres of gasoline each day (about 360 million US or 300 million imperial gallons). The US used about 510 billion litres (138 billion US gal/115 billion imp gal) of gasoline in 2006, of which 5.6% was mid-grade and 9.5% was premium grade.^[21]

Western countries have among the highest usage rates per person.^{[citation needed]}

Europe

Unlike the US, countries in Europe impose substantial taxes on fuels such as gasoline. For example, price for gasoline in Europe is more than twice that in the US.

United States

From 1998 to 2004, the price of gasoline was between $1 and $2 USD per U.S. gallon.^[22] After 2004, the price increased until the average gas price reached a high of $4.11 per U.S. gallon in mid-2008, but has receded to approximately $2.60 per U.S. gallon as of September 2009.^[22] Recently, the U.S. has experienced an upswing in gas prices of 13.51% from Jan 31st to March 7, 2011.^[23]

Unlike most consumer goods, the prices of which are listed before tax, in the United States, gasoline prices are posted with taxes included. Taxes are added by federal, state and local governments. As of 2009, the federal tax is 18.4¢ per gallon for gasoline and 24.4¢ per gallon for diesel (excluding red diesel).^[24] Among states, the highest gasoline tax rates, including the federal taxes as of 2005, are New York (62.9¢/gal), Hawaii (60.1¢/gal), and California (60¢/gal).^[23] However, many states' taxes are a percentage and thus vary in amount depending on the cost of the gasoline.

About 9% of all gasoline sold in the US in May 2009 was premium grade, according to the Energy Information Administration. Consumer Reports magazine says, “If your car can run on regular, run it on regular.”^{[citation needed]} The Associated Press said premium gas—which is a higher octane and costs several cents a gallon more than regular unleaded—should be used only if the manufacturer says it is “required”.^[25]

Etymology and terminology

"Gasoline" is cited (under the spelling "gasolene") from 1865 in the Oxford English Dictionary.^[26] The trademark Gasoline was never registered, and eventually became generic in North America and the Philippines.

The word "petrol" has been used in English to refer to raw petroleum since the 16th century.^[26] However, it was first used to refer to the refined fuel in 1892, when it was registered as a trade name by British wholesaler Carless, Capel & Leonard at the suggestion of Frederick Richard Simms, as a contraction of 'St. Peter's Oil'.^[27] Carless's competitors used the term "motor spirit" until the 1930s.^[28][29] The Oxford English Dictionary suggests this usage may have been inspired by the French pétrole.^[26]

In many countries, gasoline has a colloquial name derived from that of the chemical benzene (e.g., German Benzin, Dutch Benzine). In other countries, especially in those portions of Latin America where Spanish predominates (i.e., most of the region except Brazil), it has a colloquial name derived from that of the chemical naphtha (e.g., Argentine/Uruguaian/Paraguaian nafta).^[30] However, the standard Spanish word is "gasolina."

The terms "mogas", short for motor gasoline, or "autogas", short for automobile gasoline, are used to distinguish automobile fuel from aviation gasoline, or "avgas".^[31][32][33] In British English, gasoline can refer to a different petroleum derivative historically used in lamps, but this usage is relatively uncommon.^{[citation needed]}

See also

Energy portal

Appendix

Volumetric and mass energy density of some fuels compared with gasoline (in the rows with gross and net, they are from^[34]):

(*) Diesel fuel is not used in a gasoline engine, so its low octane rating is not an issue; the relevant metric for diesel engines is the cetane number

Notes

References

External links

Wikimedia Commons has media related to: Gasoline

Look up gasoline in Wiktionary, the free dictionary.

• CNN/Money: Global gas prices
• EEP: European gas prices
• Transportation Energy Data Book
• Energy Supply Logistics Searchable Directory of US Terminals
• 2011 NACS Annual Fuels Report
• Definition of basic terms, Graphs of Gas prices. all in Slovak language
• Gasoline from Vinegar | MIT Technology Review
• High octane fuel, leaded and LRP petrol - article from robotpig.net

Images

• "Down the Gasoline Trail" Handy Jam Organization, 1935 (Cartoon)