Proven world oil reserves, 2009.

Petroleum (L. petroleum, from Greek: petra (rock) + Latin: oleum (oil)) or crude oil is a naturally occurring, flammable liquid consisting of a complex mixture ofhydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling. This latter stage comes after studies of structural geology (at the reservoir scale), sedimentary basin analysis, reservoir characterization (mainly in terms of porosity and permeable structures). It is refined and separated, most easily by boiling point, into a large number of consumer products, from gasoline andkerosene to asphalt and chemical reagents used to make plastics and pharmaceuticals. Petroleum is often attributed as the "Mother of all Commodities" because of its importance in the manufacture of a wide variety of materials

Pumpjack pumping an oil well nearLubbock, Texas.

.The term petroleum is found (in the spelling "petraoleum") in tenth-century Old English sources. It was used in the treatise De Natura Fossilium, published in 1546 by the German mineralogist Georg Bauer, also known as Georgius Agricola. In the 19th Century, the term petroleum was frequently used to refer to mineral oils produced by distillation from mined organic solids such as cannel coal (and later oil shale), and refined oils produced from them; in the United Kingdom, storage (and later transport) of these oils were regulated by a series of Petroleum Acts, from the Petroleum Act 1862 c. 66 onward.

Composition

In its strictest sense, petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid (e.g., paraffin) hydrocarbons. Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids. However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface conditions and on the phase diagram of the petroleum mixture.

An oil well produces predominantly crude oil, with some natural gas dissolved in it. Because the pressure is lower at the surface than underground, some of the gas will come out of solution and be recovered (or burned) as associated gas or solution gas. A gas well produces predominantly natural gas. However, because the underground temperature and pressure are higher than at the surface, the gas may contain heavier hydrocarbons such as pentane, hexane, and heptane in the gaseous state. At surface conditions these will condense out of the gas to form natural gas condensate, often shortened to condensate. Condensate resembles petrol in appearance and is similar in composition to some volatile light crude oils.

The proportion of light hydrocarbons in the petroleum mixture varies greatly among different oil fields, ranging from as much as 97% by weight in the lighter oils to as little as 50% in the heavier oils and bitumens.

The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various aromatic hydrocarbons while the other organic compounds contain nitrogen, oxygen and sulfur, and trace amounts of metals such asiron, nickel, copper and vanadium. The exact molecular composition varies widely from formation to formation but the proportion of chemical elements vary over fairly narrow limits as follows:

Composition by weight

Element	Percent range
Carbon	83 to 87%
Hydrogen	10 to 14%
Nitrogen	0.1 to 2%
Oxygen	0.05 to 1.5%
Sulfur	0.05 to 6.0%
Metals	< 0.1%

Four different types of hydrocarbon molecules appear in crude oil. The relative percentage of each varies from oil to oil, determining the properties of each oil.

Composition by weight

Hydrocarbon	Average	Range
Paraffins	30%	15 to 60%
Naphthenes	49%	30 to 60%
Aromatics	15%	3 to 30%
Asphaltics	6%	remainder

Most of the world's oils are non-conventional.

Crude oil varies greatly in appearance depending on its composition. It is usually black or dark brown (although it may be yellowish, reddish, or even greenish). In the reservoir it is usually found in association with natural gas, which being lighter forms a gas cap over the petroleum, and saline water which, being heavier than most forms of crude oil, generally sinks beneath it. Crude oil may also be found in semi-solid form mixed with sand and water, as in the Athabasca oil sands in Canada, where it is usually referred to as crude bitumen. In Canada, bitumen is considered a sticky, black, tar-like form of crude oil which is so thick and heavy that it must be heated or diluted before it will flow. Venezuela also has large amounts of oil in the Orinoco oil sands, although the hydrocarbons trapped in them are more fluid than in Canada and are usually called extra heavy oil. These oil sands resources are called unconventional oil to distinguish them from oil which can be extracted using traditional oil well methods. Between them, Canada and Venezuela contain an estimated 3.6 trillion barrels (570×10⁹ m³) of bitumen and extra-heavy oil, about twice the volume of the world's reserves of conventional oil.

Petroleum is used mostly, by volume, for producing fuel oil and petrol, both important "primary energy" sources. 84% by volume of the hydrocarbons present in petroleum is converted into energy-rich fuels (petroleum-based fuels), including petrol, diesel, jet, heating, and other fuel oils, and liquefied petroleum gas. The lighter grades of crude oil produce the best yields of these products, but as the world's reserves of light and medium oil are depleted, oil refineries are increasingly having to process heavy oil and bitumen, and use more complex and expensive methods to produce the products required. Because heavier crude oils have too much carbon and not enough hydrogen, these processes generally involve removing carbon from or adding hydrogen to the molecules, and using fluid catalytic cracking to convert the longer, more complex molecules in the oil to the shorter, simpler ones in the fuels.

Due to its high energy density, easy transportability and relative abundance, oil has become the world's most important source of energy since the mid-1950s. Petroleum is also the raw material for many chemicalproducts, including pharmaceuticals, solvents, fertilizers, pesticides, and plastics; the 16% not used for energy production is converted into these other materials. Petroleum is found in porous rock formations in the upper strata of some areas of the Earth's crust. There is also petroleum in oil sands (tar sands). Known oil reserves are typically estimated at around 190 km³ (1.2 trillion (short scale) barrels) without oil sands,or 595 km³ (3.74 trillion barrels) with oil sands. Consumption is currently around 84 million barrels (13.4×10⁶ m³) per day, or 4.9 km³ per year. Which in turn yields a remaining oil supply of only about 120 years, if current demand remain static.

Chemistry

Octane, a hydrocarbon found in petroleum. Lines represent single bonds; black spheres represent carbon; white spheres represent hydrogen.

Petroleum is a mixture of a very large number of different hydrocarbons; the most commonly found molecules are alkanes (linear or branched), cycloalkanes, aromatic hydrocarbons, or more complicated chemicals like asphaltenes. Each petroleum variety has a unique mix of molecules, which define its physical and chemical properties, like color and viscosity.

The alkanes, also known as paraffins, are saturated hydrocarbons with straight or branched chains which contain only carbon and hydrogen and have the general formula C_nH_2n+2. They generally have from 5 to 40 carbon atoms per molecule, although trace amounts of shorter or longer molecules may be present in the mixture.

The alkanes from pentane (C₅H₁₂) to octane (C₈H₁₈) are refined into petrol, the ones from nonane (C₉H₂₀) to hexadecane (C₁₆H₃₄) into diesel fuel, kerosene and jet fuel). Alkanes with more than 16 carbon atoms can be refined into fuel oil and lubricating oil. At the heavier end of the range, paraffin wax is an alkane with approximately 25 carbon atoms, while asphalt has 35 and up, although these are usually cracked by modern refineries into more valuable products. The shortest molecules, those with four or fewer carbon atoms, are in a gaseous state at room temperature. They are the petroleum gases. Depending on demand and the cost of recovery, these gases are either flared off, sold as liquified petroleum gas under pressure, or used to power the refinery's own burners. During the winter, Butane (C₄H₁₀), is blended into the petrol pool at high rates, because butane's high vapor pressure assists with cold starts. Liquified under pressure slightly above atmospheric, it is best known for powering cigarette lighters, but it is also a main fuel source for many developing countries. Propane can be liquified under modest pressure, and is consumed for just about every application relying on petroleum for energy, from cooking to heating to transportation.

The cycloalkanes, also known as naphthenes, are saturated hydrocarbons which have one or more carbon rings to which hydrogen atoms are attached according to the formula C_nH_2n. Cycloalkanes have similar properties to alkanes but have higher boiling points.

The aromatic hydrocarbons are unsaturated hydrocarbons which have one or more planar six-carbon rings called benzene rings, to which hydrogen atoms are attached with the formula C_nH_n. They tend to burn with a sooty flame, and many have a sweet aroma. Some are carcinogenic.

These different molecules are separated by fractional distillation at an oil refinery to produce petrol, jet fuel, kerosene, and other hydrocarbons. For example, 2,2,4-Trimethylpentane (isooctane), widely used inpetrol, has a chemical formula of C₈H₁₈ and it reacts with oxygen exothermically:^[16]

2 C₈H₁₈(l) + 25 O₂(g) → 16 CO₂(g) + 18 H₂O(g) + 10.86 MJ/mol (of octane)

The amount of various molecules in an oil sample can be determined in laboratory. The molecules are typically extracted in a solvent, then separated in a gas chromatograph, and finally determined with a suitabledetector, such as a flame ionization detector or a mass spectrometer.^[17] Due to the large number of co-eluted hydrocarbons within oil, many cannot be resolved by traditional gas chromatography and typically appear as a hump in the chromatogram. This unresolved complex mixture (UCM) of hydrocarbons is particularly apparent when analysing weathered oils and extracts from tissues of organisms exposed to oil.

Incomplete combustion of petroleum or petrol results in production of toxic byproducts. Too little oxygen results in carbon monoxide. Due to the high temperatures and high pressures involved, exhaust gases from petrol combustion in car engines usually include nitrogen oxides which are responsible for creation of photochemical smog.

Empirical equations for the thermal properties of petroleum products

Heat of combustion

At a constant volume the heat of combustion of a petroleum product can be approximated as follows:

Q_v = 12,400 − 2,100d²

where Q_v is measured in cal/gram and d is the specific gravity at 60 °F (16 °C).

Thermal conductivity

The thermal conductivity of petroleum based liquids can be modeled as follows:

,547

where K is measured in BTU · hr⁻¹ft⁻² , t is measured in °F and d is the specific gravity at 60 °F (16 °C).

Specific heat

The specific heat of a petroleum oils can be modeled as follows:

,

where c is measured in BTU/lbm-°F, t is the temperature in Fahrenheit and d is the specific gravity at 60 °F (16 °C).

In units of kcal/(kg·°C), the formula is:

,

where the temperature t is in Celsius and d is the specific gravity at 15 °C.

Latent heat of vaporization

The latent heat of vaporization can be modeled under atmospheric conditions as follows:

,

where L is measured in BTU/lbm, t is measured in °F and d is the specific gravity at 60 °F (16 °C).

In units of kcal/kg, the formula is:

,

where the temperature t is in Celsius and d is the specific gravity at 15 °C.

Formation

Structure of vanadium porphyrin compound extracted from petroleum by Alfred E. Treibs, father of organic geochemistry. Treibs noted the close structural similarity of this molecule and chlorophyll a.

Petroleum is a fossil fuel derived from ancient fossilized organic materials, such as zooplankton and algae. Vast quantities of these remains settled to a sea or lake bottoms, mixing with sediments and being buried under anoxic conditions. As further layers settled to the sea or lake bed, intense heat and pressure built up in the lower regions. This process caused the organic matter to change, first into a waxy material known askerogen, which is found in various oil shales around the world, and then with more heat into liquid and gaseous hydrocarbons via a process known as catagenesis. Formation of petroleum occurs from hydrocarbon pyrolysis in a variety of mostly endothermic reactions at high temperature and/or pressure.

There were certain warm nutrient-rich environments such as the Gulf of Mexico and the ancient Tethys Sea where the large amounts of organic material falling to the ocean floor exceeded the rate at which it could decompose. This resulted in large masses of organic material being buried under subsequent deposits such as shale formed from mud. This massive organic deposit later became heated and transformed under pressure into oil.

Geologists often refer to the temperature range in which oil forms as an "oil window"—below the minimum temperature oil remains trapped in the form of kerogen, and above the maximum temperature the oil is converted to natural gas through the process of thermal cracking. Sometimes, oil formed at extreme depths may migrate and become trapped at a much shallower level. The Athabasca Oil Sands is one example of this.

Abiogenic origin hypothesis

A small number of geologists adhere to the abiogenic petroleum origin hypothesis, maintaining that high molecular weight hydrocarbons of purely inorganic origin exist within Earth's interior and are the source for major petroleum deposits. The hypothesis was originally proposed by Nikolai Kudryavtsev and Vladimir Porfiriev in the 1950s, and more recently Thomas Gold proposed a similar deep hot biosphere idea. The thermodynamic synthesis routes necessary to carry abiogenic source material into subsurface oil are not established, observation of organic markers in kerogen and oil is not explained, and no oil deposits have been located by this hypothesis.

Crude oil

Crude oil reservoirs

Hydrocarbon trap.

Three conditions must be present for oil reservoirs to form: a source rock rich in hydrocarbon material buried deep enough for subterranean heat to cook it into oil; a porous and permeable reservoir rock for it to accumulate in; and a cap rock (seal) or other mechanism that prevents it from escaping to the surface. Within these reservoirs, fluids will typically organize themselves like a three-layer cake with a layer of water below the oil layer and a layer of gas above it, although the different layers vary in size between reservoirs. Because most hydrocarbons are lighter than rock or water, they often migrate upward through adjacent rock layers until either reaching the surface or becoming trapped within porous rocks (known as reservoirs) by impermeable rocks above. However, the process is influenced by underground water flows, causing oil to migrate hundreds of kilometres horizontally or even short distances downward before becoming trapped in a reservoir. When hydrocarbons are concentrated in a trap, an oil field forms, from which the liquid can be extracted by drilling and pumping.

The reactions that produce oil and natural gas are often modeled as first order breakdown reactions, where hydrocarbons are broken down to oil and natural gas by a set of parallel reactions, and oil eventually breaks down to natural gas by another set of reactions. The latter set is regularly used in petrochemical plants and oil refineries.

Wells are drilled into oil reservoirs to extract the crude oil. "Natural lift" production methods that rely on the natural reservoir pressure to force the oil to the surface are usually sufficient for a while after reservoirs are first tapped. In some reservoirs, such as in the Middle East, the natural pressure is sufficient over a long time. The natural pressure in many reservoirs, however, eventually dissipates. Then the oil must be pumped out using “artificial lift” created by mechanical pumps powered by gas or electricity. Over time, these "primary" methods become less effective and "secondary" production methods may be used. A common secondary method is “waterflood” or injection of water into the reservoir to increase pressure and force the oil to the drilled shaft or "wellbore." Eventually "tertiary" or "enhanced" oil recovery methods may be used to increase the oil's flow characteristics by injecting steam, carbon dioxide and other gases or chemicals into the reservoir. In the United States, primary production methods account for less than 40% of the oil produced on a daily basis, secondary methods account for about half, and tertiary recovery the remaining 10%. Extracting oil (or “bitumen”) from oil/tar sand and oil shale deposits requires mining the sand or shale and heating it in a vessel or retort, or using “in-situ” methods of injecting heated liquids into the deposit and then pumping out the oil-saturated liquid.

Unconventional oil reservoirs

Oil-eating bacteria biodegrade oil that has escaped to the surface. Oil sands are reservoirs of partially biodegraded oil still in the process of escaping and being biodegraded, but they contain so much migrating oil that, although most of it has escaped, vast amounts are still present—more than can be found in conventional oil reservoirs. The lighter fractions of the crude oil are destroyed first, resulting in reservoirs containing an extremely heavy form of crude oil, called crude bitumen in Canada, or extra-heavy crude oil in Venezuela. These two countries have the world's largest deposits of oil sands.

On the other hand, oil shales are source rocks that have not been exposed to heat or pressure long enough to convert their trapped hydrocarbons into crude oil. Technically speaking, oil shales are not always shales and do not contain oil, but are fined-grain sedimentary rocks containing an insoluble organic solid called kerogen. The kerogen in the rock can be converted into crude oil using heat and pressure to simulate natural processes. The method has been known for centuries and was patented in 1694 under British Crown Patent No. 330 covering, "A way to extract and make great quantityes of pitch, tarr, and oyle out of a sort of stone." Although oil shales are found in many countries, the United States has the world's largest deposits.

Classification

A sample of medium heavy crude oil

The petroleum industry generally classifies crude oil by the geographic location it is produced in (e.g. West Texas Intermediate, Brent, or Oman), its API gravity (an oil industry measure of density), and its sulfur content. Crude oil may be considered light if it has low density or heavy if it has high density; and it may be referred to assweet if it contains relatively little sulfur or sour if it contains substantial amounts of sulfur.

The geographic location is important because it affects transportation costs to the refinery. Light crude oil is more desirable than heavy oil since it produces a higher yield of petrol, while sweet oil commands a higher price than sour oil because it has fewer environmental problems and requires less refining to meet sulfur standards imposed on fuels in consuming countries. Each crude oil has unique molecular characteristics which are understood by the use of crude oil assay analysis in petroleum laboratories.

Barrels from an area in which the crude oil's molecular characteristics have been determined and the oil has been classified are used as pricing references throughout the world. Some of the common reference crudes are:

• West Texas Intermediate (WTI), a very high-quality, sweet, light oil delivered at Cushing, Oklahoma for North American oil
• Brent Blend, comprising 15 oils from fields in the Brent and Ninian systems in the East Shetland Basin of the North Sea. The oil is landed at Sullom Voe terminal in Shetland. Oil production from Europe, Africa and Middle Eastern oil flowing West tends to be priced off this oil, which forms a benchmark
• Dubai-Oman, used as benchmark for Middle East sour crude oil flowing to the Asia-Pacific region
• Tapis (from Malaysia, used as a reference for light Far East oil)
• Minas (from Indonesia, used as a reference for heavy Far East oil)
• The OPEC Reference Basket, a weighted average of oil blends from various OPEC (The Organization of the Petroleum Exporting Countries) countries
• Midway Sunset Heavy, by which heavy oil in California is priced 

There are declining amounts of these benchmark oils being produced each year, so other oils are more commonly what is actually delivered. While the reference price may be for West Texas Intermediate delivered at Cushing, the actual oil being traded may be a discounted Canadian heavy oil delivered at Hardisty, Alberta, and for a Brent Blend delivered at Shetland, it may be a Russian Export Blend delivered at the port of Primorsk.