Gasoline

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"Petrol" redirects here. For other uses of these terms, see gas (disambiguation) or petrol (disambiguation)
File:Gasoline tank.jpg

Gasoline or petrol is a petroleum-derived liquid mixture consisting mostly of hydrocarbons and enhanced with benzene or iso-octane to increase octane ratings, used as fuel in internal combustion engines.

Most Commonwealth countries or former Commonwealth countries, with the exception of Canada, use the term "petrol" (abbreviated from petroleum spirit). The term "gasoline" is commonly used in North America where it is often shortened in colloquial usage to "gas". This should be distinguished in usage from genuinely gaseous fuels used in internal combustion engines such as liquified petroleum gas (which is stored pressurised as a liquid but is allowed to return naturally to a gaseous state before combustion). The term mogas, short for motor gasoline, distinguished automobile fuel from aviation gasoline, or avgas. The word "gasoline" can also be used in British English to refer to a different petroleum derivative historically used in lamps; however, this use is now uncommon.[1]

Look up gasoline in Wiktionary, the free dictionary.

History

Early uses

Before internal-combustion engines were invented in the mid 19th century, gasoline was sold in small bottles as a treatment against lice and their eggs. At that time, the word Petrol was a trade name. This treatment method is no longer common, because of the inherent fire hazard and the risk of dermatitis.

In the U.S., gasoline was also sold as a cleaning fluid to remove grease stains from clothing. Before dedicated filling stations were established, early motorists would buy gasoline in cans to fill their tanks.

The name gasoline is similar to that of other petroleum products of the day, most notably petroleum jelly, a highly purified heavy distillate, which was branded Vaseline. The trademark Gasoline, however, was never registered, and thus became generic.

Gasoline was also used in kitchen ranges and for lighting, and is still available in a highly purified form, known as camping fuel or white gas, for use in lanterns and portable stoves.

During the Franco-Prussian War (1870–1871), pétrole was stockpiled in Paris for use against a possible German-Prussian attack on the city. Later in 1871, during the revolutionary Paris Commune, rumours spread around the city of pétroleuses, women using bottles of petrol to commit arson against city buildings.

Etymology

The word "gasolene" was coined in 1865 from the word gas and the chemical suffix -ine/-ene. The modern spelling was first used in 1871. The shortened form "gas" was first recorded in American English in 1905.[1] Gasoline originally referred to any liquid used as the fuel for a gasoline-powered engine, other than diesel fuel or liquefied gas. Methanol racing fuel would have been classed as a type of gasoline.[2]

The word "petrol" was first used in reference to the refined substance as early as 1892 (it previously referred to unrefined petroleum), and was registered as a trade name by German wholesaler Carless, Capel & Leonard. Although it was never officially registered as a trademark, Carless's competitors used the term "Motor Spirit" until the 1930s. [3] [4]

Bertha Benz used chemist shops to purchase the gasoline for her famous drive from Mannheim to Pforzheim in 1888. In Germany, gasoline is called Benzin. The usage does not derive from Bertha Benz, but from the chemical benzene.

Chemical analysis and production

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.

The bulk of a typical gasoline consists of hydrocarbons with between 5 and 12 carbon atoms per molecule.

Many of these hydrocarbons are considered hazardous substances and are regulated in the United States by OSHA. The MSDS (Material Safety Data Sheet) for unleaded gasoline shows at least fifteen hazardous chemicals occurring in various amounts from 5% to 35% by volume of gasoline. These include big names like benzene (up to 5% by volume), toluene (up to 35% by volume), naphthalene (up to 1% by volume), trimethylbenzene (up to 7% by volume), MTBE (up to 18% by volume) and about 10 others. Ref: (Tesoro Petroleum Companies, Inc. [5])

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

  • Reformate, produced in a catalytic reformer with a high octane rating and high aromatic content, and very low olefins (alkenes).
  • 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. Here, "cat" is short for "catalyst".
  • 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 ocatane 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), aromatics 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 used by the refinery on a particular day.
  • the grade of gasoline, in particular the octane rating.

Currently many countries set tight limits on gasoline aromatics in general, benzene in particular, and olefins (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.

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 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.

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, the volatility limit changes every month and differs for each main distribution center, but 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 non-reformulated 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 [6]. 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.[7]

Octane rating

Further information: octane rating

The most important characteristic of gasoline is its octane rating, which is a measure of how resistant gasoline is to premature detonation in an internal combustion engine, also known as knocking. It is measured relative to a mixture of 2,2,4-trimethylpentane (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.

World War II and octane ratings

World War II Germany received much of its oil from Romania. From 2.8 million barrels in 1938, Romania’s exports to Germany increased to 13 million barrels by 1941, a level that was essentially maintained through 1942 and 1943, before dropping by half, due to Allied bombing and mining of the Danube. Although these exports were almost half of Romania’s total production, they were considerably less than what the Germans expected. Even with the addition of the Romanian deliveries, overland oil imports after 1939 could not make up for the loss of overseas shipments. In order to become less dependent on outside sources, the Germans undertook a sizable expansion program of their own meager domestic oil pumping. After 1938, the Austrian oil fields were made available and the expansion of Nazi crude oil output was chiefly concentrated there. Primarily as a result of this expansion, the Reich's domestic output of crude oil increased from approximately 3.8 million barrels in 1938 to almost 12 million barrels in 1944. Even this was not enough.

Instead, Germany had developed a synthetic fuel capacity that was intended to replace imported or captured oil. Fuels were generated from Coal, using either the Bergius process or the Fischer-Tropsch process. Between 1938 and 1943, synthetic fuel output underwent a respectable growth from 10 million barrels to 36 million. The percentage of synthetic fuels compared to the yield from all sources grew from 22 percent to more than 50 percent by 1943. The total oil supplies available from all sources for the same period rose from 45 million barrels in 1938 to 71 million barrels in 1943.

By the early 1930s, automobile gasoline had an octane reading of 40 and aviation gasoline of 75-80. Aviation gasoline with such high octane numbers could only be refined through a process of distillation of high-grade petroleum. Germany’s domestic oil was not of this quality. Only the lead additive tetraethyl could raise the octane to a maximum of 87. The license for the production of this additive was acquired in 1935 from the American holder of the patents, but without high-grade Romanian oil even this additive was not very effective.

In the US the oil was not "as good" and the oil industry had to invest heavily in various expensive boosting systems. This turned out to have benefits: the US industry started delivering fuels of increasing octane ratings by adding more of the boosting agents and the infrastructure was in place for a post-war octane agents additive industry. Good crude oil was no longer a factor during wartime and by war's end, American aviation fuel was commonly 130 to 150 octane. This high octane could easily be used in existing engines to deliver much more power by increasing the pressure delivered by the superchargers. The Germans, relying entirely on "good" gasoline, had no such industry, and instead had to rely on ever-larger engines to deliver more power.

However, German aviation engines were of the direct fuel injection type and could use methanol-water injection and nitrous oxide injection, which gave 50% more engine power for five minutes of dogfight. This could be done only five times or after 40 hours run-time and then the engine would have to be rebuilt. Most German aero engines used 87 octane fuel (called B4), while some high-powered engines used 100 octane (C2/C3) fuel.

This historical "issue" is based on a very common misapprehension about wartime fuel octane numbers. There are two octane numbers for each fuel, one for lean mix and one for rich mix, rich being always greater. So, for example, a common British aviation fuel of the later part of the war was 100/125. The misapprehension that German fuels have a lower octane number (and thus a poorer quality) arises because the Germans quoted the lean mix octane number for their fuels while the Allies quoted the rich mix number for their fuels. Standard German high-grade aviation fuel used in the later part of the war (given the designation C3) had lean/rich octane numbers of 100/130. The Germans would list this as a 100 octane fuel while the Allies would list it as 130 octane.

After the war the US Navy sent a Technical Mission to Germany to interview German petrochemists and examine German fuel quality. Their report entitled Technical Report 145-45 Manufacture of Aviation Gasoline in Germany chemically analyzed the different fuels and concluded that "Toward the end of the war the quality of fuel being used by the German fighter planes was quite similar to that being used by the Allies".

Energy content

Gasoline contains about 34.6 megajoules per litre (MJ/l) or 131 MJ/US gallon. This is an average, gasoline blends differ, therefore actual energy content varies from season to season and from batch to batch, as much as 4% more or less than the average, according to the US EPA.


Volumetric energy density of some fuels compared to gasoline:[2]

Fuel type      MJ/L      MJ/kg     BTU/Imp gal     BTU/US gal     Research octane
number (RON)
Regular Gasoline 34.8 ~47 150,100 125,000 Min 91
Premium Gasoline Min 95
Autogas (LPG) (60% Propane + 40% Butane)
Ethanol 23.5 31.1[3] 101,600 84,600 129
Methanol 17.9 19.9 77,600 64,600 123
Gasohol (10% ethanol + 90% gasoline) 33.7 145,200 120,900 93/94
Diesel 38.60 166,600 138,700 25(*)
Aviation gasoline 33.5 46.8 144,400 120,200
Liquefied natural gas 25.3 ~55 109,000 90,800

(*) Diesel 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

A high octane fuel such as LPG has a lower energy content than lower octane gasoline, resulting in an overall lower power output at the regular compression ratio an engine ran at on gasoline. However, with an engine tuned to the use of LPG (ie. 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 - this means less space in a cylinder on its combustion stroke, hence a higher cylinder temperature which improves efficiency according to Carnot's theorem, along with fewer wasted hydrocarbons (therefore less pollution and wasted energy), bringing higher power levels coupled with less pollution overall because of the greater efficiency.

The main reason for the lower energy content (per litre) of LPG in comparison to gasoline is that it has a lower density. Energy content per kilogram is higher than for gasoline (higher hydrogen to carbon ratio). The weight-density of gasoline is about 737.22 kg/m3.

Different countries have some variation in what RON (Research Octane Number) is standard for gasoline, or petrol. 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 hi-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 fuels can vary between 86-87 AKI (91-92 RON) for regular, through 89-90 (94-95) for mid-grade (European Premium), up to 90-94 (RON 95-99) for premium unleaded or E10 (Super in Europe)

Additives

Main article: Gasoline additive

Lead

The mixture known as gasoline, when used in high compression internal combustion engines, has a tendency to ignite early (pre-ignition or detonation) causing a 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 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 US automobiles since 1975, this practice began to wane 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 U.S., where lead was 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 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 United States. However, fuel containing lead may continue to be sold for off-road uses, including aircraft, racing cars, farm equipment, and marine engines until 2008. 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.[8] [9]

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.

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, Europe and the Middle East, leaded gasoline is still in use. Leaded gasoline was phased out in sub-Saharan Africa with effect from 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, and a large Canadian study concluded that MMT impairs the effectiveness of automobile emission controls and increases pollution from motor vehicles.

Dye

Main article: Fuel dyes

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), 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 mandatory. For example, in Southern California, fuel must contain 2% oxygen by weight. 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[10].

MTBE use is being phased out in some states due to issues with contamination of ground water. In some places 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 often 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. Over 3,400 million US gallons (13,000,000 m³) of ethanol mostly produced from corn was produced in the United States in 2004 for fuel use, and E85 is fast becoming available in much of the United States. 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 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.)

Health concerns

Many of the non-aliphatic hydrocarbons naturally present in gasoline (especially aromatic ones like benzene), as well as many anti-knocking additives, are carcinogenic. Because of this, any large-scale or ongoing leaks of gasoline pose a threat to the public's health and the environment, should the gasoline reach a public supply of drinking water. 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. Gasoline is rather volatile (meaning it readily evaporates), requiring that storage tanks on land and in vehicles be properly sealed. The high volatility also means that it will easily ignite in cold weather conditions, unlike diesel for example. Appropriate venting is needed to ensure the level of pressure is similar on the inside and outside. Gasoline also reacts dangerously with certain common chemicals; for example, gasoline and crystal Drāno (sodium hydroxide) react together in a spontaneous combustion.

Gasoline is also one of the sources of pollutant gases. Even gasoline which does not contain lead or sulfur compounds produces carbon dioxide, nitrogen oxides, and carbon monoxide in the exhaust of the engine which is running on it. Furthermore, 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.

Through misuse as an inhalant, gasoline also contributes to damage to health. Petrol sniffing is a common way of obtaining a high for many people and has become epidemic in many poorer communities such as with Indigenous Australians and Canadians. In response, Opal fuel has been developed by the BP Kwinana Refinery in Australia, and contains only 5% aromatics (unlike the usual 25%) which inhibits the effects of inhalation.

Usage and pricing

Main article: Gasoline usage and pricing

The United States uses 360 million US liquid gallons (1.36 gigalitres) of gasoline each day. Western countries have among the highest usage rates per person. Some countries, e.g. in Europe and Japan, impose heavy fuel taxes on fuels such as gasoline. Because a greater proportion of the price of gasoline in the United States is due to the cost of oil, rather than taxes, the price of the retail product is subject to greater fluctuations (vs. outside the U.S.) when calculated as a percentage of cost-per-unit, but is actually less variable in absolute terms.

Stability

When gasoline is left for a certain period of time, gums and varnishes may build up and precipitate in the gasoline, causing "stale fuel." This will cause gums to build up in the cylinders and also the fuel lines, making it harder to start the engine. Gums and varnishes should be removed by a professional to extend engine life. Motor gasoline may be stored up to 60 days in an approved container. If it is to be stored for a longer period of time, a fuel stabilizer may be used. This will extend the life of the fuel to about 1-2 years, and keep it fresh for the next uses. Fuel stabilizer is commonly used for small engines such as lawnmower and tractor engines to promote quicker and more reliable starting.

Substitutes

Main article: Alternative fuel

See also

Notes

  1. ^ Refer to the Oxford English Dictionary
  2. ^ Appendix B, Transportation Energy Data Book from the Center for Transportation Analysis of the Oak Ridge National Laboratory
  3. ^ Calculated from heats of formation. Does not correspond exactly to the figure for MJ/L divided by density.

References

External links

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