INTRODUCTION TO ALTERNATIVE FUELS

Alternative fuels, known as non-conventional or advanced fuels, are any materials or substances that can be used as fuels, other than conventional fuels. Conventional fuels include: fossil fuels (petroleum (oil), coal, and natural gas), as well as nuclear materials such as uranium and thorium, as well as artificial radioisotope fuels that are made in nuclear reactors.
Some well-known alternative fuels include biodiesel, bioalcohol (methanol, ethanol, and butanol), chemically stored electricity (batteries and fuel cells), hydrogen, non-fossil methane, non-fossil natural gas, vegetable oil, propane, and other biomass sources.

Background

The main purpose of fuel is to store energy, which should be in a stable form and can be easily transported to the place of use. Almost all fuels are chemical fuels. The user employs this fuel to generate heat or perform mechanical work, such as powering an engine. It may also be used to generate electricity, which is then used for heating, lighting, or other purpose.

Biofuel

Main article: Biofuel

Biofuels are also considered a renewable source. Although renewable energy is used mostly to generate electricity, it is often assumed that some form of renewable energy or a percentage is used to create alternative fuels.

Biomass

Main article: Biomass

Biomass in the energy production industry is living and recently dead biological material which can be used as fuel or for industrial production.

Algae-based fuels

Main article: Algae fuel

Algae-based biofuels have been promoted in the media as a potential panacea to crude oil-based transportation problems. Algae could yield more than 2000 gallons of fuel per acre per year of production. Algae based fuels are being successfully tested by the U.S. Navy. Algae-based plastics show potential to reduce waste and the cost per pound of algae plastic is expected to be cheaper than traditional plastic prices.

Biodiesel

Biodiesel is made from animal fats or vegetable oils, renewable resources that come from plants such as, jatropha, soybean, sunflowers, corn, olive, peanut, palm, coconut, safflower, canola, sesame, cottonseed, etc. Once these fats or oils are filtered from their hydrocarbons and then combined with alcohol like methanol, biodiesel is brought to life ^[from this chemical reaction. These raw materials can either be mixed with pure diesel to make various proportions, or used alone. Despite one’s mixture preference, biodiesel will release smaller number of pollutants (carbon monoxide particulates and hydrocarbons) than conventional diesel, because biodiesel burns both cleanly and more efficiently. Even with regular diesel’s reduced quantity of sulfur from the ULSD (ultra-low sulfur diesel) invention, biodiesel exceeds those levels because it is sulfur-free.

Alcohol fuels

Main articles: Alcohol fuel, Butanol fuel, Ethanol fuel and Methanol fuel

Methanol and ethanol fuel are primary sources of energy; they are convenient fuels for storing and transporting energy. These alcohols can be used in internal combustion engines as alternative fuels. Butanol has another advantage: it is the only alcohol-based motor fuel that can be transported readily by existing petroleum-product pipeline networks, instead of only by tanker trucks and railroad cars.

Ammonia

Ammonia (NH₃) can be used as fuel. Benefits of ammonia include no need for oil, zero emissions, low cost, and distributed production reducing transport and related pollution.

Carbon-neutral and negative fuels

Carbon neutral fuel is synthetic fuel—such as methane, gasoline, diesel fuel or jet fuel—produced from renewable or nuclear energy used to hydrogenate waste carbon dioxide recycled from power plant flue exhaust gas or derived from carbonic acid in seawater. To the extent that carbon neutral fuels displace fossil fuels, or if they are produced from waste carbon or seawater carbonic acid, and their combustion is subject to carbon capture at the flue or exhaust pipe, they result in negative carbon dioxide emission and net carbon dioxide removal from the atmosphere, and thus constitute a form of greenhouse gas remediation. Such carbon neutral and negative fuels can be produced by the electrolysis of water to make hydrogen used in the Sabatier reaction to produce methane which may then be stored to be burned later in power plants as synthetic natural gas, transported by pipeline, truck, or tanker ship, or be used in gas to liquids processes such as the Fischer–Tropsch process to make traditional transportation or heating fuels.

Carbon-neutral fuels have been proposed for distributed storage for renewable energy, minimizing problems of wind and solar intermittency, and enabling transmission of wind, water, and solar power through existing natural gas pipelines. Such renewable fuels could alleviate the costs and dependency issues of imported fossil fuels without requiring either electrification of the vehicle fleet or conversion to hydrogen or other fuels, enabling continued compatible and affordable vehicles. Germany has built a 250-kilowatt synthetic methane plant which they are scaling up to 10 megawatts. Audi has constructed a carbon neutral liquefied natural gas (LNG) plant in Werlte, Germany. The plant is intended to produce transportation fuel to offset LNG used in their A3 Sportback g-tron automobiles, and can keep 2,800 metric tons of CO₂ out of the environment per year at its initial capacity. Other commercial developments are taking place in Columbia, South Carolina, Camarillo, California, and Darlington, England.

Nighttime wind power is considered the most economical form of electrical power with which to synthesize fuel, because the load curve for electricity peaks sharply during the warmest hours of the day, but wind tends to blow slightly more at night than during the day. Therefore, the price of nighttime wind power is often much less expensive than any alternative. Off-peak wind power prices in high wind penetration areas of the U.S. averaged 1.64 cents per kilowatt-hour in 2009, but only 0.71 cents/kWh during the least expensive six hours of the day. Typically, wholesale electricity costs 2 to 5 cents/kWh during the day. Commercial fuel synthesis companies suggest they can produce fuel for less than petroleum fuels when oil costs more than $55 per barrel. The U.S. Navy estimates that shipboard production of jet fuel from nuclear power would cost about $6 per gallon. While that was about twice the petroleum fuel cost in 2010, it is expected to be much less than the market price in less than five years if recent trends continue. Moreover, since the delivery of fuel to a carrier battle group costs about $8 per gallon, shipboard production is already much less expensive. However, U.S. civilian nuclear power is considerably more expensive than wind power. The Navy's estimate that 100 megawatts can produce 41,000 gallons of fuel per day indicates that terrestrial production from wind power would cost less than $1 per gallon.

Hydrogen

Main article: Hydrogen fuel

Hydrogen is an emissionless fuel. The byproduct of hydrogen burning is water, although some mono-nitrogen oxides NOx are produced when hydrogen is burned with air.

HCNG

Main article: HCNG

HCNG (or H2CNG) is a mixture of compressed natural gas and 4-9 percent hydrogen by energy.

Liquid nitrogen

Liquid nitrogen is another type of emissionless fuel.

Compressed air

The air engine is an emission-free piston engine using compressed air as fuel. Unlike hydrogen, compressed air is about one-tenth as expensive as fossil oil, making it an economically attractive alternative fuel.

Natural Gas Vehicles

Compressed natural gas (CNG) and Liquefied Natural Gas (LNG) are two a cleaner combusting alternatives to conventional liquid automobile fuels.

CNG Fuel Types

CNG vehicles can use both renewable CNG and non-renewable CNG.

Conventional CNG is produced from the many underground natural gas reserves are in widespread production worldwide today. New technologies such as horizontal drilling and hydraulic fracturing to economically access unconventional gas resources appear to have increased the supply of natural gas in a fundamental way.

Renewable natural gas or biogas is a methane‐based gas with similar properties to natural gas that can be used as transportation fuel. Present sources of biogas are mainly landfills, sewage, and animal/agri‐waste. Based on the process type, biogas can be divided into the following: Biogas produced by anaerobic digestion, Landfill gas collected from landfills, treated to remove trace contaminants, and Synthetic Natural Gas (SNG).

Practicality

Around the world, this gas powers more than 5 million vehicles, and just over 150,000 of these are in the U.S. American usage is growing at a dramatic rate.

Environmental Analysis

Because natural gas emits little pollutant when combusted, cleaner air quality has been measured in urban localities switching to natural gas vehicles Tailpipe CO2 can be reduced by 15‐25% compared to gasoline, diesel. The greatest reductions occur in medium and heavy duty, light duty and refuse truck segments.

CO2 reductions of up to 88% are possible by using biogas.

Similarities to Hydrogen Natural gas, like hydrogen, is another fuel that burns cleanly; cleaner than both gasoline and diesel engines. Also, none of the smog-forming contaminates are emitted. Hydrogen and Natural Gas are both lighter than air and can be mixed together.

Nuclear power and radiothermal generators

Main articles: Nuclear power and radiothermal generator

Nuclear reactors

Nuclear power is any nuclear technology designed to extract usable energy from atomic nuclei via controlled nuclear reactions. The only controlled method now practical uses nuclear fission in a fissile fuel (with a small fraction of the power coming from subsequent radioactive decay). Use of the nuclear reaction nuclear fusion for controlled power generation is not yet practical, but is an active area of research.

Nuclear power is usually used by using a nuclear reactor to heat a working fluid such as water, which is then used to create steam pressure, which is converted into mechanical work for the purpose of generating electricity or propulsion in water. Today, more than 15% of the world's electricity comes from nuclear power, and over 150 nuclear-powered naval vessels have been built.

In theory, electricity from nuclear reactors could also be used for propulsion in space, but this has yet to be demonstrated in a space flight. Some smaller reactors, such as the TOPAZ nuclear reactor, are built to minimize moving parts, and use methods that convert nuclear energy to electricity more directly, making them useful for space missions, but this electricity has historically been used for other purposes. Power from nuclear fission has been used in a number of spacecraft, all of them unmanned. The Soviets up to 1988 orbited 33 nuclear reactors in RORSAT military radar satellites, where electric power generated was used to power a radar unit that located ships on the Earth's oceans. The U.S. also orbited one experimental nuclear reactor in 1965, in the SNAP-10A mission. No nuclear reactor has been sent into space since 1988.

Radiothermal generators

In addition, radioisotopes have been used as alternative fuels, on both land and in space. Their use on land is declining due to the danger of theft of isotope and environmental damage if the unit is opened. The decay of radioisotopes generates both heat and electricity in many space probes, particularly probes to outer planets where sunlight is weak and low temperatures is a problem. Radiothermal generators (RTGs) which use such radioisotopes as fuels do not sustain a nuclear chain reaction, but rather generate electricity from the decay of a radioisotope which has (in turn) been produced on Earth as a concentrated power source (fuel) using energy from an Earth-based nuclear reactor.

                                                 

                                                            METHANOL

Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH₃OH (often abbreviated MeOH). Methanol acquired the name "wood alcohol" because it was once produced chiefly as a byproduct of the destructive distillation of wood. Modern methanol is produced in a catalytic industrial process directly from carbon monoxide, carbon dioxide, and hydrogen.
Methanol is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to that of ethanol (drinking alcohol). However, unlike ethanol, methanol is highly toxic and unfit for consumption. At room temperature, it is a polar liquid, and is used as an antifreeze, solvent, fuel, and as a denaturant for ethanol. It is also used for producing biodiesel via transesterification reaction.
Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria, and is commonly present in small amounts in the environment. As a result, there is a small fraction of methanol vapor in the atmosphere. Over the course of several days, atmospheric methanol is oxidized with the help of sunlight to carbon dioxide and water.
Methanol burns in oxygen, including open air, forming carbon dioxide and water:

2 CH₃OH + 3 O₂ → 2 CO₂ + 4 H₂O

Methanol ingested in large quantities is metabolized to formic acid or formate salts, which is poisonous to the central nervous system, and may cause blindness, coma, and death. Because of these toxic properties, methanol is frequently used as a denaturant additive for ethanol manufactured for industrial uses. This addition of methanol exempts industrial ethanol (commonly known as "denatured alcohol" or "methylated spirit") from liquor excise taxation in the US and some other countries.

Occurrence

Human metabolite

Main article: Alcohol § Toxicity

Methanol is poisonous to the central nervous system and may cause blindness, coma, and death. However, small amount of methanol is a natural endogenous compound found in normal, healthy human individuals, concluded by one study which found a mean of 4.5 ppm in the exhaled breath of the subjects. The mean endogenous methanol in humans of 0.45 g/d may be metabolized from pectin found in fruit; One kilogram of apple produces up to 1.4 gram methanol.

Toxicity

Methanol has a high toxicity in humans. If as little as 10 mL of pure methanol is ingested, for example, it can break down into formic acid, which can cause permanent blindness by destruction of the optic nerve, and 30 mL is potentially fatal, although the median lethal dose is typically 100 mL (3.4 fl oz) (i.e. 1–2 mL/kg body weight of pure methanol). Reference dose for methanol is 0.5 mg/kg/day. Toxic effects take hours to start, and effective antidotes can often prevent permanent damage. Because of its similarities in both appearance and odor to ethanol (the alcohol in beverages), it is difficult to differentiate between the two (such is also the case with denatured alcohol). However, there are cases of methanol resistance, such as that of Mike Malloy, who was the victim of a failed murder attempt by methanol in the early 1930s.

Methanol is toxic by two mechanisms. First, methanol (whether it enters the body by ingestion, inhalation, or absorption through the skin) can be fatal due to its CNS depressant properties in the same manner as ethanol poisoning. Second, in a process of toxication, it is metabolized to formic acid (which is present as the formate ion) via formaldehyde in a process initiated by the enzyme alcohol dehydrogenize in the liver. Methanol is converted to formaldehyde via alcohol dehydrogenize (ADH) and formaldehyde is converted to formic acid (formate) via aldehyde dehydrogenize (ALDH). The conversion to formate via ALDH proceeds completely, with no detectable formaldehyde remaining. Formate is toxic because it inhibits mitochondrial cytochrome c oxidize, causing the symptoms of hypoxia at the cellular level, and also causing metabolic acidosis, among a variety of other metabolic disturbances.

Methanol poisoning can be treated with the antidotes ethanol or fomepizole. Both drugs act to reduce the action of alcohol dehydrogenize on methanol by means of competitive inhibition, so it is excreted by the kidneys rather than being transformed into toxic metabolites. Further treatment may include giving sodium bicarbonate for metabolic acidosis, and hemodialysis or hemodiafiltration can be used to remove methanol and formate from the blood. Folinic acid or folic acid is also administered to enhance the metabolism of formate.

The initial symptoms of methanol intoxication include central nervous system depression, headache, dizziness, nausea, lack of coordination, and confusion. Sufficiently large doses can cause unconsciousness and death. The initial symptoms of methanol exposure are usually less severe than the symptoms resulting from the ingestion of a similar quantity of ethanol. Once the initial symptoms have passed, a second set of symptoms arises, 10 to as many as 30 hours after the initial exposure to methanol, including blurring or complete loss of vision, acidosis and putaminal hemorrhages, an uncommon but serious complication. These symptoms result from the accumulation of toxic levels of formate in the blood, and may progress to death by respiratory failure. Physical examination may show tachypnea, and ophthalmologic examination may show dilated pupils with hyperemia of the optic disc and retinal edema. Small amounts of methanol are produced by the metabolism of food and are generally harmless, being metabolized quickly and completely.

Ethanol is sometimes denatured (adulterated), and made poisonous, by the addition of methanol. The result is known as methylated spirit, "meths" (British use) or "metho" (Australian slang). These are not to be confused with "meth", a common abbreviation for methamphetamine, and an abbreviation for methadone in Britain.

Applications

Methanol, a common laboratory solvent, is especially useful for HPLC, UV/VIS spectroscopy, and LCMS due to its low UV cutoff.

Feedstock

The largest use of methanol by far is in making other chemicals. About 40% of methanol is converted to formaldehyde, and from there into products as diverse as plastics, plywood, paints, explosives, and permanent press textiles.

Also in the early 1970s, a methanol to gasoline process was developed by Mobil for producing gasoline ready for use in vehicles. One such industrial facility was built at Motunui in New Zealand in the 1980s. In the 1990s, large amounts of methanol were used in the United States to produce the gasoline additive methyl tert-butyl ether (MTBE). While MTBE is no longer marketed in the U.S., it is still widely used in other parts of the world. In addition to direct use as a fuel, methanol (or less commonly, ethanol) is used as a component in the transesterification of triglycerides to yield a form of biodiesel.

Other chemical derivatives of methanol include dimethyl ether, which has replaced chlorofluorocarbons as an aerosol spray propellant, and acetic acid. Dimethyl ether (DME) also can be blended with liquified petroleum gas (LPG) for home heating and cooking, and can be used as a diesel replacement for transportation fuel.

Methanol-to-Olefins/Methanol-to-Propylene (MTO/MTP), among others processes such as: Metathesis, Propane Dehydrogenation (PDH), High Severity FCC, and Olefins Cracking, is a new and novel lower-cost chemical process for on-purpose propylene production technology of high interest to the petrochemical marketplace, to supply the tight market for propylene.

The market became tight because of the ethane prices falling in the USA, due to the exploration of shale gas reserves. The low price ethylene produced from this raw material has given chemical producers in North America a feedstock advantage. Such change has put naphtha-fed steam crackers at a disadvantageous position, with many of them shutting down or revamping to use ethane as feedstock. Nevertheless, the propylene output rates from ethane-fed crackers are negligible.

Fuel for vehicles

Main articles: Methanol fuel and methanol economy

Methanol is used on a limited basis to fuel internal combustion engines. Pure methanol is required by rule to be used in Champcars, Monster Trucks, USAC sprint cars (as well as midgets, modifieds, etc.), and other dirt track series, such as World of Outlaws, and Motorcycle Speedway. Methanol is also used, as the primary fuel ingredient since the late 1940s, in the powerplants for radio control, control line and free flight airplanes (as methanol is required in the engines that primarily power them), cars and trucks, from such an engine's use of a platinum filament glow plug being able to ignite the methanol vapor through a catalytic reaction. Drag racers and mud racers, as well as heavily modified tractor pullers, also use methanol as their primary fuel source. Methanol is required with a supercharged engine in a Top Alcohol Dragster and, until the end of the 2006 season, all vehicles in the Indianapolis 500 had to run methanol. Mud racers have mixed methanol with gasoline with nitrous oxide to produce more power than mixing gasoline and nitrous oxide alone.

One of the potential drawbacks of using high concentrations of methanol (and other alcohols, such as ethanol) in fuel is the corrosivity to some metals of methanol, particularly to aluminium. Methanol, although a weak acid, attacks the oxide coating that normally protects the aluminum from corrosion:

6 CH₃OH + Al₂O₃ → 2 Al(OCH₃)₃ + 3 H₂O

The resulting methoxide salts are soluble in methanol, resulting in a clean aluminium surface, which is readily oxidized by dissolved oxygen. Also, the methanol can act as an oxidizer:

6 CH₃OH + 2 Al → 2 Al(OCH₃)₃ + 3 H₂

This reciprocal process effectively fuels corrosion until either the metal is eaten away or the concentration of CH₃OH is negligible. Concerns with methanol's corrosivity have been addressed by using methanol-compatible materials, and fuel additives that serve as corrosion inhibitors.

When produced from wood or other organic materials, the resulting organic methanol (bioalcohol) has been suggested as renewable alternative to petroleum-based hydrocarbons. Low levels of methanol can be used in existing vehicles, with the use of proper cosolvents and corrosion inhibitors.

Methanol fuel has been proposed for ground transportation. The chief advantage of a methanol economy is that it could be adapted to present internal combustion engines with a minimum of modification in both engines and infrastructure to store and deliver liquid fuel.

Government policy

The European Fuel Quality Directive allows up to 3% methanol with an equal amount of cosolvent to be blending in gasoline sold in Europe. China uses more than one billion gallons of methanol per year as a transportation fuel in both low level blends used in existing vehicles, and as high level blends in vehicles designed to accommodate the use of methanol fuels.

In the USA in 2011, the Open Fuel Standard Act of 2011 was introduced in the US Congress to encourage car manufacturers to warrant their cars to burn methanol as a fuel in addition to gasoline and ethanol. The bill is being championed by the Open Fuel Standard Coalition.

Other applications

Methanol is a traditional denaturant for ethanol, the product being known as "denatured alcohol" or "methylated spirit". This was commonly used during the Prohibition to discourage consumption of bootlegged liquor, and ended up causing several deaths.

Methanol is also used as a solvent, and as an antifreeze in pipelines and windshield washer fluid.

In some wastewater treatment plants, a small amount of methanol is added to wastewater to provide a carbon food source for the denitrifying bacteria, which convert nitrates to nitrogen to reduce the nitrification of sensitive aquifers.

During World War II, methanol was used as a fuel in several German military rocket designs, under the name M-Stoff, and in a roughly 50/50 mixture with hydrazine, known as C-Stoff.

Methanol was used as an automobile coolant antifreeze in the early 1900s.

Methanol is used as a denaturing agent in polyacrylamide gel electrophoresis.

Direct-methanol fuel cells are unique in their low temperature, atmospheric pressure operation, allowing them to be miniaturized to an unprecedented degree. This, combined with the relatively easy and safe storage and handling of methanol, may open the possibility of fuel cell-powered consumer electronics, such as for laptop computers and mobile phones.

Methanol is also a widely used fuel in camping and boating stoves. Methanol burns well in an unpressurized burner, so alcohol stoves are often very simple, sometimes little more than a cup to hold fuel. This lack of complexity makes them a favorite of hikers who spend extended time in the wilderness. Similarly, the alcohol can also be gelled to reduce risk of leaking or spilling, as with the brand "Sterno".

Methanol is mixed with water and injected into high performance diesel and gasoline engines for an increase of power and a decrease in intake air temperature in a process known as water methanol injection.

Energy carrier

Methanol is also useful as an energy carrier. It is easier to store than hydrogen, burns cleaner than fossil fuels, and is biodegradable.

Safety in automotive fuels

Pure methanol has been used in open wheel auto racing since the mid-1960s. Unlike petroleum fires, methanol fires can be extinguished with plain water. A methanol-based fire burns invisibly, unlike gasoline, which burns with a visible flame. If a fire occurs on the track, there is no flame or smoke to obstruct the view of fast approaching drivers, but this can also delay visual detection of the fire and the initiation of fire suppression. The decision to permanently switch to methanol in American IndyCar racing was a result of the devastating crash and explosion at the 1964 Indianapolis 500, which killed drivers Eddie Sachs and Dave MacDonald. In 2007 IndyCars switched to ethanol.

Methanol is readily biodegradable in both aerobic (oxygen present) and anaerobic (oxygen absent) environments. Methanol will not persist in the environment. The half-life for methanol in groundwater is just one to seven days, while many common gasoline components have half-lives in the hundreds of days (such as benzene at 10–730 days). Since methanol is miscible with water and biodegradable, it is unlikely to accumulate in groundwater, surface water, air or soil.

Production

From synthesis gas

Carbon monoxide and hydrogen react over a catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966. At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from carbon monoxide and hydrogen with high selectivity (>99.8%):

CO + 2 H₂ → CH₃OH

It is worth noting that the production of synthesis gas from methane produces three moles of hydrogen gas for every mole of carbon monoxide, while the methanol synthesis consumes only two moles of hydrogen gas per mole of carbon monoxide. One way of dealing with the excess hydrogen is to inject carbon dioxide into the methanol synthesis reactor, where it, too, reacts to form methanol according to the equation:

CO₂ + 3 H₂ → CH₃OH + H₂O

Some chemists believe that the certain catalysts synthesize methanol using CO₂ as an intermediary, and consuming CO only indirectly.

CO₂ + 3 H₂ → CH₃OH + H₂O

where the H₂O byproduct is recycled via the water-gas shift reaction

CO + H₂O → CO₂ + H₂,

This gives an overall reaction, which is the same as listed above.

CO + 2 H₂ → CH₃OH

From methane

The direct catalytic conversion of methane to methanol using Cu-zeolites or other catalysts is an alternative process for the efficient production of methanol.

From carbon dioxide

Methanol has been generated directly from carbon dioxide in solution using copper oxide (CuO) nanorods coated by cuprous oxide (Cu₂O) and energy from (simulated) sunlight. The process operated with 95% electrochemical efficiency and is claimed to be scalable to industrial size.

Feedstocks

Production of synthesis gas

Originally, synthesis gas for the production of methanol came from coal. Today, synthesis gas is most commonly produced from the methane component in natural gas, because natural gas contains hydrogen. Three processes are commercially practiced. At moderate pressures of 4 MPa (40 atm) and high temperatures (around 850 °C), methane reacts with steam on a nickel catalyst to produce syngas according to the chemical equation:

CH₄ + H₂O → CO + 3 H₂

This reaction, commonly called steam-methane reforming or SMR, is endothermic, and the heat transfer limitations place limits on the size of and pressure in the catalytic reactors used. Methane can also undergo partial oxidation with molecular oxygen (at atmospheric pressure) to produce syngas, as the following equation shows:

2 CH₄ + O₂ → 2 CO + 4 H₂

This reaction is exothermic, and the heat given off can be used in-situ to drive the steam-methane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The high pressures and high temperatures needed for steam-reforming require a greater capital investment in equipment than is needed for a simple partial-oxidation process; however, the energy-efficiency of steam-reforming is higher than for partial-oxidation, unless the waste-heat from partial-oxidation is used.

Stoichiometry adjustment

Stoichiometry for methanol production requires the ratio of H₂ / CO to equal 2. The partial oxidation process yields a ratio of 2, and the steam reforming process yields a ratio of 3. The H₂ / CO ratio can be lowered to some extent by the reverse water-gas shift reaction,

CO₂ + H₂ → CO + H₂O,

to provide the appropriate stoichiometry for methanol synthesis.

Although natural gas is the most economical and widely used feedstock for methanol production, many other feedstocks can be used to produce syngas via steam reforming. Steam-reformed coal is sometimes used as a feedstock for methanol production, particularly in China. In addition, mature technologies available for biomass gasification are being used for methanol production. For instance, woody biomass can be gasified to water gas (a hydrogen-rich syngas), by introducing a blast of steam in a blast furnace. The water-gas / syngas can then be synthesized to methanol using standard methods. The net process is carbon neutral, since the CO₂ byproduct is required to produce biomass via photosynthesis. Using a composition for wood of 50% carbon, 42% oxygen, 6% hydrogen we can represent wood with the formula C₁₁H₁₆O₇ (we could also use C₈H₁₂O₅). Then some combination of the following two formal reactions will occur:

3 C₁₁H₁₆O₇ + 22 H₂O → 46 H₂ + 23 CO + 10 CO₂ → 23 CH₃OH + 10 CO₂

2 C₁₁H₁₆O₇ + 11 O₂ → 16 H₂ + 8 CO + 14 CO₂ → 8 CH₃OH + 14 CO₂

Quality specifications and analysis

Methanol for laboratory use

Methanol is available commercially in various purity grades for fine chemicals: 1) “Synthesis” quality (corresponding to normal commercial methanol) 2) Certified analytical quality 3) Extremely pure qualities for semiconductor manufacture

Commercial methanol

In addition to laboratory grades, commercial methanol is generally classified according to ASTM purity grades A and AA. Methanol for chemical use normally corresponds to Grade AA. In addition to water, typical impurities include acetone (which is very difficult to separate by distillation) and ethanol. When methanol is delivered by ships or tankers used to transport other substances, contamination by the previous cargo must be expected. Comparative ultraviolet spectroscopy has proved a convenient, quick test method for deciding whether a batch can be accepted and loaded.Traces of all chemicals derived from aromatic parent substances, as well as a large number of other compounds, can be detected. Further tests for establishing the quality of methanol include measurements of boiling point range, density, permanganate number, turbidity, color index, and acid number. More comprehensive tests include water determination according to the Karl Fischer method and gas chromatographic determination of byproducts. However, the latter is relatively expensive and time consuming because several injections using different columns and detectors must be made due to the variety of byproducts present.

History

In their embalming process, the ancient Egyptians used a mixture of substances, including methanol, which they obtained from the pyrolysis of wood. Pure methanol, however, was first isolated in 1661 by Robert Boyle, when he produced it via the distillation of buxus (boxwood).^[32] It later became known as "pyroxylic spirit". In 1834, the French chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition.

They also introduced the word "methylene" to organic chemistry, forming it from Greek methy = "wine" + hȳlē = wood (patch of trees), with Greek language errors: "wood (substance)" (Greek xylon) was intended, and the components are in the wrong order for Greek. The term "methyl" was derived in about 1840 by back-formation from "methylene", and was then applied to describe "methyl alcohol". This was shortened to "methanol" in 1892 by the International Conference on Chemical Nomenclature. The suffix -yl used in organic chemistry to form names of carbon groups, was extracted from the word "methyl".

In 1923, the German chemists Alwin Mittasch and Mathias Pier, working for BASF, developed a means to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide, and hydrogen) into methanol. A patent was filed 12 January 1926 (reference no. 1,569,775). This process used a chromium and manganese oxide catalyst, and required extremely vigorous conditions—pressures ranging from 50 to 220 atm, and temperatures up to 450 °C. Modern methanol production has been made more efficient through use of catalysts (commonly copper) capable of operating at lower pressures. The modern low pressure methanol (LPM) was developed by ICI in the late 1960s with the technology now owned by Johnson Matthey, which is a leading licensor of methanol technology.

Methanol is one of the most heavily traded chemical commodities in the world, with an estimated global demand of around 27 to 29 million metric tons. In recent years, production capacity has expanded considerably, with new plants coming on-stream in South America, China and the Middle East, the latter based on access to abundant supplies of methane gas. Even though nameplate production capacity (coal-based) in China has grown significantly, operating rates are estimated to be as low as 50 to 60%. No new production capacity is scheduled to come on-stream until 2015.

The main applications for methanol are the production of formaldehyde (used in construction and wooden boarding), acetic acid (basis for a.o. PET-bottles), MTBE (fuel component and replacement for the very volatile diethyl ether) and more recently for the formation of methyl esters in the production of bio-diesel. In China, demand is expected to grow exponentially, not only caused by a growing internal market of the traditional applications, but accelerated by new applications, such as direct blending (with gasoline), Methanol-To-Olefins (e.g. propylene) and DME. Methanol can also be used to produce gasoline.

The use of methanol as a motor fuel received attention during the oil crises of the 1970s due to its availability, low cost, and environmental benefits. By the mid-1990s, over 20,000 methanol "flexible fuel vehicles" capable of operating on methanol or gasoline were introduced in the U.S. In addition, low levels of methanol were blended in gasoline fuels sold in Europe during much of the 1980s and early-1990s. Automakers stopped building methanol FFVs by the late-1990s, switching their attention to ethanol-fueled vehicles. While the methanol FFV program was a technical success, rising methanol pricing in the mid- to late-1990s during a period of slumping gasoline pump prices diminished the interest in methanol fuels.

                   

                                  ETHANOL

Commonly referred to simply as alcohol or spirits, ethanol /ˈɛθənɒl/ is also called ethyl alcohol, and drinking alcohol. It is the principal type of alcohol found in alcoholic beverages, produced by the fermentation of sugars by yeasts. It is a neurotoxic psychoactive drug and one of the oldest recreational drugs used by humans. It can cause alcohol intoxication when consumed in sufficient quantity. Ethanol is used as a solvent, an antiseptic, a fuel and the active fluid in modern (post-mercury) thermometers. It is a volatile, flammable, colorless liquid with the structural formula CH3CH2OH, often abbreviated as C2H5OH or C2H6O.

Etymology

Ethanol is the systematic name defined by the International Union of Pure and Applied Chemistry (IUPAC) for a molecule with two carbon atoms (prefix "eth-"), having a single bond between them (suffix "-ane"), and an attached functional group-OH group (suffix "-ol").
The prefix ethyl was coined in 1834 by the German chemist Justus Liebig. Ethyl is a contraction of the French word ether (any substance that evaporated or sublimated readily at room temperature) and the Greek word ύλη (hyle, substance).
The name ethanol was coined as a result of a resolution that was adopted at the International Conference on Chemical Nomenclature that was held in April 1892 in Geneva, Switzerland.
The term "alcohol" now refers to a wider class of substances in chemistry nomenclature, but in common parlance it remains the name of ethanol. Ultimately a medieval loan from Arabic al-kuḥl, use of alcohol in this sense is modern, introduced in the mid 18th century. Before that time, Middle Latin alcohol referred to "powdered ore of antimony; powdered cosmetic", by the later 17th century "any sublimated substance; distilled spirit" use for "the spirit of wine" (shortened from a full expression alcohol of wine) recorded 1753. The systematic use in chemistry dates to 1850.

Chemical formula

Ethanol is a 2-carbon alcohol. Its molecular formula is CH₃CH₂OH. An alternative notation is CH₃–CH₂–OH, which indicates that the carbon of a methyl group (CH₃–) is attached to the carbon of a methylene group (–CH₂–), which is attached to the oxygen of a hydroxyl group (–OH). It is a constitutional isomer of dimethyl ether. Ethanol is sometimes abbreviated as EtOH, using the common organic chemistry notation of representing the ethyl group (C₂H₅) with Et.

Natural occurrence

Ethanol is a byproduct of the metabolic process of yeast. As such, ethanol will be present in any yeast habitat. Ethanol can commonly be found in overripe fruit. Ethanol produced by symbiotic yeast can be found in Bertam Palm blossoms. Although some animal species such as the Pentailed Treeshrew exhibit ethanol-seeking behaviors, most show no interest or avoidance of food sources containing ethanol. Ethanol is also produced during the germination of many plants as a result of natural anerobiosis. Ethanol has been detected in outer space, forming an icy coating around dust grains in interstellar clouds. Minute quantity amounts (244 ppb) of endogenous ethanol and acetaldehyde were found in the exhaled breath of healthy volunteers.

Pharmacology

Activity profile

Ethanol is known to possess the following direct pharmacodynamic actions:

• GABA_A receptor positive allosteric modulator (primarily of δ subunit-containing receptors)
• NMDA receptor negative allosteric modulator
• Glycine receptor positive and negative allosteric modulator
• 5-HT₃ receptor positive allosteric modulator
• nACh receptor positive and negative allosteric modulator
• L-type calcium channel blocker
• GIRK channel opener
• Glycine reuptake inhibitor Adenosine reuptake inhibitor

Some of its actions on ligand-gated ion channels, specifically the nACh receptors and the glycine receptor, are dose-dependent, with potentiation or inhibition occurring dependent on ethanol concentration. This is because ethanol's effects on these channels are a summation of positive and negative allosteric modulatory actions.

Properties

The removal of ethanol from the human body, through oxidation by alcohol dehydrogenase in the liver, is limited. Hence, the removal of a large concentration of alcohol from blood may follow zero-order kinetics. This means that alcohol leaves the body at a constant rate, rather than having an elimination half-life.
The rate-limiting steps for one substance may be in common with other substances. As a result, the blood alcohol concentration can be used to modify the rate of metabolism of methanol and ethylene glycol. Methanol itself is not highly toxic, but its metabolites formaldehyde and formic acid are; therefore, to reduce the rate of production and concentration of these harmful metabolites, ethanol can be ingested. Ethylene glycol poisoning can be treated in the same way.
Pure ethanol will irritate the skin and eyes. Nausea, vomiting and intoxication are symptoms of ingestion. Long-term use by ingestion can result in serious liver damage. Atmospheric concentrations above one in a thousand are above the European Union Occupational exposure limits.

Short-term

Main article: Short-term effects of alcohol

BAC (g/L)	BAC (% v/v)	Symptoms
0.5	0.05%	Euphoria, talkativeness, relaxation
1	0.1 %	Central nervous system depression, nausea, possible vomiting, impaired motor and sensory function, impaired cognition
>1.4	>0.14%	Decreased blood flow to brain
3	0.3%	Stupefaction, possible unconsciousness
4	0.4%	Possible death
>5.5	>0.55%	Death

Effects on the central nervous system

Ethanol is a central nervous system depressant and has significant psychoactive effects in sublethal doses; for specifics, see "Effects of alcohol on the body by dose". Based on its abilities to change the human consciousness, ethanol is considered a psychoactive drug. Death from ethanol consumption is possible when blood alcohol level reaches 0.4%. A blood level of 0.5% or more is commonly fatal. Levels of even less than 0.1% can cause intoxication, with unconsciousness often occurring at 0.3–0.4%.
The amount of ethanol in the body is typically quantified by blood alcohol content (BAC), which is here taken as weight of ethanol per unit volume of blood. The table at the right summarizes the symptoms of ethanol consumption. Small doses of ethanol, in general, produce euphoria and relaxation; people experiencing these symptoms tend to become talkative and less inhibited, and may exhibit poor judgment. At higher dosages (BAC > 1 g/L), ethanol acts as a central nervous system depressant, producing at progressively higher dosages, impaired sensory and motor function, slowed cognition, stupefaction, unconsciousness, and possible death.
Ethanol acts in the central nervous system primarily by binding to the GABA_A receptor, increasing the effects of the inhibitory neurotransmitter GABA (i.e., it is a positive allosteric modulator).
Prolonged heavy consumption of alcohol can cause significant permanent damage to the brain and other organs. See Alcohol consumption and health.
According to the US National Highway Traffic Safety Administration, in 2002 about "41% of people fatally injured in traffic crashes were in alcohol related crashes". The risk of a fatal car accident increases exponentially with the level of alcohol in the driver's blood. Most drunk driving laws governing the acceptable levels in the blood while driving or operating heavy machinery set typical upper limits of blood alcohol content (BAC) between 0.02% and 0.08%.
Discontinuing consumption of alcohol after several years of heavy drinking can also be fatal. Alcohol withdrawal can cause anxiety, autonomic dysfunction, seizures, and hallucinations. Delirium tremens is a condition that requires people with a long history of heavy drinking to undertake an alcohol detoxification regimen.
The reinforcing effects of alcohol consumption are also mediated by acetaldehyde generated by catalase and other oxidizing enzymes such as cytochrome P-4502E1 in the brain. Although acetaldehyde has been associated with some of the adverse and toxic effects of ethanol, it appears to play a central role in the activation of the mesolimbic dopamine system.

Effects on metabolism

Main articles: Ethanol metabolism and Alcohol dehydrogenase

Ethanol within the human body is converted into acetaldehyde by alcohol dehydrogenase and then into the acetyl in acetyl CoA by acetaldehyde dehydrogenase. Acetyl CoA is the final product of both carbohydrate and fat metabolism, where the acetyl can be further used to produce energy or for biosynthesis. As such, ethanol can be compared to an energy-bearing macronutrient, yielding approximately 7 kcal per gram consumed. However, the product of the first step of this breakdown, acetaldehyde, is more toxic than ethanol. Acetaldehyde is linked to most of the clinical effects of alcohol. It has been shown to increase the risk of developing cirrhosis of the liver and multiple forms of cancer.
During the metabolism of alcohol via the respective dehydrogenases, NAD (Nicotinamide adenine dinucleotide) is converted into reduced NAD. Normally, NAD is used to metabolise fats in the liver, and as such alcohol competes with these fats for the use of NAD. Prolonged exposure to alcohol means that fats accumulate in the liver, leading to the term 'fatty liver'. Continued consumption (such as in alcoholism) then leads to cell death in the hepatocytes as the fat stores reduce the function of the cell to the point of death. These cells are then replaced with scar tissue, leading to the condition called cirrhosis.

Drug interactions

Ethanol can intensify the sedation caused by other central nervous system depressant drugs such as barbiturates, benzodiazepines, opioids, non-benzodiazepines (such as Zolpidem and Zopiclone), antipsychotics, sedative antihistamines, and antidepressants. It interacts with cocaine in vivo to produce cocaethylene, another psychoactive substance. Ethanol enhances the bioavailability of methylphenidate (elevated plasma d-MPH). In combination with cannabis, ethanol increases plasma THC levels, which suggets that ethanol may increase the absorption of THC.
Alcohol and metronidazole
One of the most important drug/food interactions that should be noted is between alcohol and metronidazole.
Metronidazole is an antibacterial agent that kills bacteria by damaging cellular DNA and hence cellular function. Metronidazole is usually given to people who have diarrhea caused by Clostridium difficile bacteria. C. difficile is one of the most common microorganisms that cause diarrhea and can lead to complications such as colon inflammation and even more severely, death.
Patients who are taking metronidazole are strongly advised to avoid alcohol, even after 1 hour after the last dose. The reason is that alcohol and metronidazole can lead to side effects such as flushing, headache, nausea, vomiting, abdominal cramps, and sweating. These symptoms are often called the disulfiram-like reaction. The proposed mechanism of action for this interaction is that metronidazole can bind to an enzyme that normally metabolizes alcohol. Binding to this enzyme may impair the liver's ability to process alcohol for proper excretion.

Alcohol and digestion

Digestive system

A part of ethyl alcohol is hydrophobic. This hydrophobic or lipophilic end can diffuse across cells that line the stomach wall. In fact, alcohol is one of the rare substances that can be absorbed in the stomach. Most food substances are absorbed in the small intestine. However, even though alcohol can be absorbed in the stomach, it is mostly absorbed in the small intestine because the small intestine has a large surface area that promotes absorption. Once alcohol is absorbed in the small intestine, it delays the release of stomach contents from emptying into the small intestine. Thus, alcohol can delay the rate of absorption of nutrients. After absorption, alcohol reaches the liver where it is metabolized.
Breathalyzers
Alcohol that is not processed by the liver goes to the heart. The liver can process only a certain amount of alcohol per unit time. Thus, when a person drinks too much alcohol, more alcohol can reach the heart. In the heart, alcohol reduces the force of heart contractions. Consequently, the heart will pump less blood, lowering overall body blood pressure. Also, blood that reaches the heart goes to the lungs to replenish blood's oxygen concentration. It is at this stage that a person can breathe out traces of alcohol. This is the underlying principle of the alcohol breath testing (or breathalyzers) to determine if a driver has been drinking and driving.
From the lungs, blood returns to the heart and will be distributed throughout the body. Interestingly, alcohol increases levels of high-density lipoproteins(HDLs), which carry cholesterol. Alcohol is known to make blood less likely to clot, reducing risk of heart attack and stroke. This could be the reason why alcohol could produce health benefits when consumed in moderate amounts. Also, alcohol dilates blood vessels. Consequently, a person will feel warmer, and their face turns flush and pink.
Loss of balance
When alcohol reaches the brain, it has the ability to delay signals that are sent between nerve cells that control balance, thinking and movement.
Frequent urination
Moreover, alcohol can affect the brain's ability to produce antidiuretic hormones. These hormones are responsible for controlling the amount of urine that is produced. Alcohol prevents the body from reabsorbing water, and consequently a person who recently drank alcohol will urinate frequently.

Alcohol and gastrointestinal diseases

Diagram of mucosal layer

Alcohol stimulates gastric juice production, even when food is not present. In other words, when a person drinks alcohol, the alcohol will stimulate stomach's acidic secretions that are intended to digest protein molecules. Consequently, the acidity has potential to harm the inner lining of the stomach. Normally, the stomach lining is protected by a mucus layer that prevents any acids from reaching the stomach cells.
However, in patients who have a peptic ulcer disease (PUD), this mucus layer is broken down. PUD is commonly associated with a bacteria H. pylori. H. pylori secretes a toxin that weakens the mucosal wall. As a result, acid and protein enzymes penetrate the weakened barrier. Because alcohol stimulates a person's stomach to secrete acid, a person with PUD should avoid drinking alcohol on an empty stomach. Drinking alcohol would cause more acid release to damage the weakened stomach wall. Complications of this disease could include a burning pain in the abdomen, bloating and in severe cases, the presence of dark black stools indicate internal bleeding. A person who drinks alcohol regularly is strongly advised to reduce their intake to prevent PUD aggravation.

Magnitude of effects

Some individuals have less effective forms of one or both of the metabolizing enzymes, and can experience more severe symptoms from ethanol consumption than others. However, those having acquired alcohol tolerance have a greater quantity of these enzymes, and metabolize ethanol more rapidly.

Long-term

Main article: Long-term effects of alcohol

Birth defects

Ethanol is classified as a teratogen. See fetal alcohol syndrome and fetal alcohol spectrum disorder.

Cancer

IARC list ethanol in alcoholic beverages as Group 1 carcinogens and arguments "There is sufficient evidence for the carcinogenicity of acetaldehyde (the major metabolite of ethanol) in experimental animals.".

Other effects

Frequent drinking of alcoholic beverages has been shown to be a major contributing factor in cases of elevated blood levels of triglycerides.
Ethanol is also widely used, clinically and over the counter, as an antitussive agent.

History

For more details on this topic, see Distilled beverage.

The fermentation of sugar into ethanol is one of the earliest biotechnologies employed by humans. The intoxicating effects of ethanol consumption have been known since ancient times. Ethanol has been used by humans since prehistory as the intoxicating ingredient of alcoholic beverages. Dried residue on 9,000-year-old pottery found in China suggests that Neolithic people consumed alcoholic beverages.
Although distillation was well known by the early Greeks and Arabs, the first recorded production of alcohol from distilled wine was by the School of Salerno alchemists in the 12th century. The first to mention absolute alcohol, in contrast with alcohol-water mixtures, was Raymond Lull.
In 1796, German-Russian chemist Johann Tobias Lowitz obtained pure ethanol by mixing partially purified ethanol (the alcohol-water azeotrope) with an excess of anhydrous alkali and then distilling the mixture over low heat. French chemist Antoine Lavoisier described ethanol as a compound of carbon, hydrogen, and oxygen, and in 1807 Nicolas-Théodore de Saussure determined ethanol's chemical formula. Fifty years later, Archibald Scott Couper published the structural formula of ethanol. It was one of the first structural formulas determined.
Ethanol was first prepared synthetically in 1825 by Michael Faraday. He found that sulfuric acid could absorb large volumes of coal gas. He gave the resulting solution to Henry Hennell, a British chemist, who found in 1826 that it contained "sulphovinic acid" (ethyl hydrogen sulfate). In 1828, Hennell and the French chemist Georges-Simon Sérullas independently discovered that sulphovinic acid could be decomposed into ethanol. Thus, in 1825 Faraday had unwittingly discovered that ethanol could be produced from ethylene (a component of coal gas) by acid-catalyzed hydration, a process similar to current industrial ethanol synthesis.
Ethanol was used as lamp fuel in the United States as early as 1840, but a tax levied on industrial alcohol during the Civil War made this use uneconomical. The tax was repealed in 1906. Use as an automotive fuel dates back to 1908, with the Ford Model T able to run on petrol(gasoline) or ethanol. It remains a common fuel for spirit lamps.
Ethanol intended for industrial use is often produced from ethylene. Ethanol has widespread use as a solvent of substances intended for human contact or consumption, including scents, flavorings, colorings, and medicines. In chemistry, it is both a solvent and a feedstock for the synthesis of other products. It has a long history as a fuel for heat and light, and more recently as a fuel for internal combustion engines.

Properties

Physical properties

Ethanol is a volatile, colorless liquid that has a slight odor. It burns with a smokeless blue flame that is not always visible in normal light.
The physical properties of ethanol stem primarily from the presence of its hydroxyl group and the shortness of its carbon chain. Ethanol's hydroxyl group is able to participate in hydrogen bonding, rendering it more viscous and less volatile than less polar organic compounds of similar molecular weight, such as propane.
Ethanol is slightly more refractive than water, having a refractive index of 1.36242 (at λ=589.3 nm and 18.35 °C or 65.03 °F).^[65]
The triple point for ethanol is 150 K at a pressure of 4.3 × 10⁻⁴ Pa.

Solvent properties

Ethanol is a versatile solvent, miscible with water and with many organic solvents, including acetic acid, acetone, benzene, carbon tetrachloride, chloroform, diethyl ether, ethylene glycol, glycerol, nitromethane, pyridine, and toluene. It is also miscible with light aliphatic hydrocarbons, such as pentane and hexane, and with aliphatic chlorides such as trichloroethane and tetrachloroethylene.
Ethanol's miscibility with water contrasts with the immiscibility of longer-chain alcohols (five or more carbon atoms), whose water miscibility decreases sharply as the number of carbons increases. The miscibility of ethanol with alkanes is limited to alkanes up to undecane: mixtures with dodecane and higher alkanes show a miscibility gap below a certain temperature (about 13 °C for dodecane). The miscibility gap tends to get wider with higher alkanes and the temperature for complete miscibility increases.
Ethanol-water mixtures have less volume than the sum of their individual components at the given fractions. Mixing equal volumes of ethanol and water results in only 1.92 volumes of mixture. Mixing ethanol and water is exothermic, with up to 777 J/mol being released at 298 K.
Mixtures of ethanol and water form an azeotrope at about 89 mole-% ethanol and 11 mole-% water or a mixture of about 96 volume percent ethanol and 4% water at normal pressure and T = 351 K. This azeotropic composition is strongly temperature- and pressure-dependent and vanishes at temperatures below 303 K.
Hydrogen bonding causes pure ethanol to be hygroscopic to the extent that it readily absorbs water from the air. The polar nature of the hydroxyl group causes ethanol to dissolve many ionic compounds, notably sodium and potassium hydroxides, magnesium chloride, calcium chloride, ammonium chloride, ammonium bromide, and sodium bromide. Sodium and potassium chlorides are slightly soluble in ethanol. Because the ethanol molecule also has a nonpolar end, it will also dissolve nonpolar substances, including most essential oils and numerous flavoring, coloring, and medicinal agents.
The addition of even a few percent of ethanol to water sharply reduces the surface tension of water. This property partially explains the "tears of wine" phenomenon. When wine is swirled in a glass, ethanol evaporates quickly from the thin film of wine on the wall of the glass. As the wine's ethanol content decreases, its surface tension increases and the thin film "beads up" and runs down the glass in channels rather than as a smooth sheet.

Flammability

An ethanol-water solution that contains 40% ABV (alcohol by volume) will catch fire if heated to about 26 °C (79 °F) and if an ignition source is applied to it. This is called its flash point. The flash point of pure ethanol is 16.60 °C (61.88 °F), less than average room temperature. The flash points of ethanol concentrations from 10% ABV to 96% ABV are shown below:

• 10% — 49 °C (120 °F)
• 20% — 36 °C (97 °F)
• 30% — 29 °C (84 °F)
• 40% — 26 °C (79 °F)
• 50% — 24 °C (75 °F)
• 60% — 22 °C (72 °F)
• 70% — 21 °C (70 °F)
• 80% — 20 °C (68 °F)
• 90% — 17 °C (63 °F)
• 96% — 17 °C (63 °F)

Alcoholic beverages that have a low concentration of ethanol will burn if sufficiently heated and an ignition source (such as an electric spark or a match) is applied to them. For example, the flash point of ordinary wine containing 12.5% ethanol is about 52 °C (126 °F).
Dishes using burning alcohol for culinary effects are called Flambé.

Production

Ethanol is produced both as a petrochemical, through the hydration of ethylene and, via biological processes, by fermenting sugars with yeast. Which process is more economical depends on prevailing prices of petroleum and grain feed stocks.

Ethylene hydration

Ethanol for use as an industrial feedstock or solvent (sometimes referred to as synthetic ethanol) is made from petrochemical feed stocks, primarily by the acid-catalyzed hydration of ethylene, represented by the chemical equation

C2H4 + H2O → CH3CH2OH

The catalyst is most commonly phosphoric acid, adsorbed onto a porous support such as silica gel or diatomaceous earth. This catalyst was first used for large-scale ethanol production by the Shell Oil Company in 1947. The reaction is carried out with an excess of high pressure steam at 300 °C (572 °F). In the U.S., this process was used on an industrial scale by Union Carbide Corporation and others, but now only LyondellBasell uses it commercially.
In an older process, first practiced on the industrial scale in 1930 by Union Carbide, but now almost entirely obsolete, ethylene was hydrated indirectly by reacting it with concentrated sulfuric acid to produce ethyl sulfate, which was hydrolyzed to yield ethanol and regenerate the sulfuric acid:

C2H4 + H2SO4 → CH3CH2SO4HCH3CH2SO4H + H2O → CH3CH2OH + H2SO4

Fermentation

Main article: Ethanol fermentation

Ethanol for use in alcoholic beverages, and the vast majority of ethanol for use as fuel, is produced by fermentation. When certain species of yeast (e.g., Saccharomyces cerevisiae) metabolize sugar in reduced-oxygen conditions they produce ethanol and carbon dioxide. The chemical equations below summarize the conversion:

C6H12O6 → 2 CH3CH2OH + 2 CO₂C12H22O11 + H2O → 4 CH3CH2OH + 4 CO₂

Fermentation is the process of culturing yeast under favorable thermal conditions to produce alcohol. This process is carried out at around 35–40 °C (95–104 °F). Toxicity of ethanol to yeast limits the ethanol concentration obtainable by brewing; higher concentrations, therefore, are usually obtained by fortification or distillation. The most ethanol-tolerant strains of yeast can survive up to approximately 18% ethanol by volume (Red Star Pasteur Champagne wine yeast, Lalvin EC-1118 wine yeast) and 20% or greater using "Turbo Yeast" as sold for spirit and fuel distillation.
To produce ethanol from starchy materials such as cereal grains, the starch must first be converted into sugars. In brewing beer, this has traditionally been accomplished by allowing the grain to germinate, or malt, which produces the enzyme amylase. When the malted grain is mashed, the amylase converts the remaining starches into sugars. For fuel ethanol, the hydrolysis of starch into glucose can be accomplished more rapidly by treatment with dilute sulfuric acid, fungally produced amylase, or some combination of the two.

Cellulose

Main article: Cellulosic ethanol

Sugars for ethanol fermentation can be obtained from cellulose. Until recently, however, the cost of the cellulase enzymes capable of hydrolyzing cellulose has been prohibitive. The Canadian firm Iogen brought the first cellulose-based ethanol plant on-stream in 2004. Its primary consumer so far has been the Canadian government, which, along with the United States Department of Energy, has invested heavily in the commercialization of cellulosic ethanol. Deployment of this technology could turn a number of cellulose-containing agricultural by-products, such as corncobs, straw, and sawdust, into renewable energy resources. Other enzyme companies are developing genetically engineered fungi that produce large volumes of cellulase, xylanase, and hemicellulase enzymes. These would convert agricultural residues such as corn stover, wheat straw, and sugar cane bagasse and energy crops such as switchgrass into fermentable sugars.
Cellulose-bearing materials typically contain other polysaccharides, including hemicellulose. Hydrolysis of hemicellulose gives mostly five-carbon sugars such as xylose. S. cerevisiae, the yeast most commonly used for ethanol production, cannot metabolize xylose. Other yeasts and bacteria are under investigation to ferment xylose and other pentoses into ethanol.

Hydrocarbon

A process developed and marketed by Celanese Corporation under the name TCX Technology uses hydrocarbons such as natural gas or coal for ethanol production rather than using fermented crops such as corn or sugarcane.

Testing

Infrared reflection spectra of liquid ethanol, showing the -OH band centered at ~3300 cm⁻¹ and C-H

 Breweries and biofuel plants employ two methods for measuring ethanol concentration. Infrared ethanol sensors measure the vibrational frequency of dissolved ethanol using the CH band at 2900 cm⁻¹. This method uses a relatively inexpensive solid state sensor that compares the CH band with a reference band to calculate the ethanol content. The calculation makes use of the Beer-Lambert law. Alternatively, by measuring the density of the starting material and the density of the product, using a hydrometer, the change in specific gravity during fermentation indicates the alcohol content. This inexpensive and indirect method has a long history in the beer brewing industry.

Research

Further information: Ethanol research

Research on ethanol production includes working from alternative source materials, novel catalysts and new chemical processes.

Purification

Distillation

Ethylene hydration or brewing produces an ethanol–water mixture. For most industrial and fuel uses, the ethanol must be purified. Fractional distillation can concentrate ethanol to 95.6% by volume (89.5 mole%). This mixture is an azeotrope with a boiling point of 78.1 °C (172.6 °F), and cannot be further purified by distillation. Addition of an entraining agent, such as benzene, cyclohexane, or heptane, allows a new ternary azeotrope comprising the ethanol, water, and the entraining agent to be formed. This lower-boiling ternary azeotrope is removed preferentially, leading to water-free ethanol.
At pressures less than atmospheric pressure, the composition of the ethanol-water azeotrope shifts to more ethanol-rich mixtures, and at pressures less than 70 torr (9.333 kPa), there is no azeotrope, and it is possible to distill absolute ethanol from an ethanol-water mixture. While vacuum distillation of ethanol is not presently economical, pressure-swing distillation is a topic of current research. In this technique, a reduced-pressure distillation first yields an ethanol-water mixture of more than 95.6% ethanol. Then, fractional distillation of this mixture at atmospheric pressure distills off the 95.6% azeotrope, leaving anhydrous ethanol at the bottom.

Molecular sieves and desiccants

Molecular sieves can be used to selectively absorb the water from the 95.6% ethanol solution. Synthetic zeolite in pellet form can be used, as well as a variety of plant-derived absorbents, including cornmeal, straw, and sawdust. The zeolite bed can be regenerated essentially an unlimited number of times by drying it with a blast of hot carbon dioxide. Cornmeal and other plant-derived absorbents cannot readily be regenerated, but where ethanol is made from grain, they are often available at low cost. Absolute ethanol produced this way has no residual benzene, and can be used to fortify port and sherry in traditional winery operations.
Apart from distillation, ethanol may be dried by addition of a desiccant, such as molecular sieves, cellulose, and cornmeal. The desiccants can be dried and reused.

Membranes and reverse osmosis

Membranes can also be used to separate ethanol and water. Membrane-based separations are not subject to the limitations water-ethanol azeotrope because separation is not based on vapor-liquid equilibria. Membranes are often used in the so-called hybrid membrane distillation process. This process uses a pre-concentration distillation column as first separating step. The further separation is then accomplished with a membrane operated either in vapor permeation or pervaporation mode. Vapor permeation uses a vapor membrane feed and pervaporation uses a liquid membrane feed.

Other techniques

A variety of other techniques have been discussed, including the following:

• Liquid-liquid extraction of ethanol from an aqueous solution;
• Extraction of ethanol from grain mash by supercritical carbon dioxide;
• Pervaporation;
• Pressure swing adsorption.

Grades of ethanol

Ethanol is available in a range of purities that result from its production or, in the case of denatured alcohol, are introduced intentionally.

Denatured alcohol

Main article: Denatured alcohol

Pure ethanol and alcoholic beverages are heavily taxed as psychoactive drugs, but ethanol has many uses that do not involve consumption by humans. To relieve the tax burden on these uses, most jurisdictions waive the tax when an agent has been added to the ethanol to render it unfit to drink. These include bittering agents such as denatonium benzoate and toxins such as methanol, naphtha, and pyridine. Products of this kind are called denatured alcohol.

Absolute alcohol

Absolute or anhydrous alcohol refers to ethanol with a low water content. There are various grades with maximum water contents ranging from 1% to a few parts per million (ppm) levels. Absolute alcohol is not intended for human consumption. If azeotropic distillation is used to remove water, it will contain trace amounts of the material separation agent (e.g. benzene). Absolute ethanol is used as a solvent for laboratory and industrial applications, where water will react with other chemicals, and as fuel alcohol. Spectroscopic ethanol is an absolute ethanol with a low absorbance in ultraviolet and visible light, fit for use as a solvent in ultraviolet-visible spectroscopy.
Pure ethanol is classed as 200 proof in the U.S., equivalent to 175 degrees proof in the UK system.

Rectified spirits

Rectified spirit, an azeotropic composition of 96% ethanol containing 4% water, is used instead of anhydrous ethanol for various purposes. Wine spirits are about 94% ethanol (188 proof). The impurities are different from those in 95% (190 proof) laboratory ethanol.

Reactions

For more details on this topic, see Alcohol.

Ethanol is classified as a primary alcohol, meaning that the carbon its hydroxyl group attaches to has at least two hydrogen atoms attached to it as well. Many ethanol reactions occur at its hydroxyl group.

Ester formation

In the presence of acid catalysts, ethanol reacts with carboxylic acids to produce ethyl esters and water:

RCOOH + HOCH₂CH₃ → RCOOCH₂CH₃ + H₂O

This reaction, which is conducted on large scale industrially, requires the removal of the water from the reaction mixture as it is formed. Esters react in the presence of an acid or base to give back the alcohol and a salt. This reaction is known as saponification because it is used in the preparation of soap. Ethanol can also form esters with inorganic acids. Diethyl sulfate and triethyl phosphate are prepared by treating ethanol with sulfur trioxide and phosphorus pentoxide respectively. Diethyl sulfate is a useful ethylating agent in organic synthesis. Ethyl nitrite, prepared from the reaction of ethanol with sodium nitrite and sulfuric acid, was formerly used as a diuretic.

Dehydration

Strong acid desiccants cause the partial dehydration of ethanol to form diethyl ether and other byproducts. If the dehydration temperature exceeds around 160 °C (320 °F), full dehydration will occur and ethylene will be the main product.

2 CH₃CH₂OH → CH₃CH₂OCH₂CH₃ + H₂O (ca. 120 °C)

   CH₃CH₂OH → H2C=CH2 + H₂O (above 160 °C)

Combustion

Complete combustion of ethanol forms carbon dioxide and water:

C₂H₅OH (l) + 3 O₂ (g) → 2 CO₂ (g) + 3 H₂O (liq); −ΔH_c = 1371 kJ/mol^[98] = 29.8 kJ/g = 327 kcal/mol = 7.1 kcal/g

C₂H₅OH (l) + 3 O₂ (g) → 2 CO₂ (g) + 3 H₂O (g); −ΔH_c = 1236 kJ/mol = 26.8 kJ/g = 295.4 kcal/mol = 6.41 kcal/g

Specific heat = 2.44 kJ/(kg·K)

Acid-base chemistry

Ethanol is a neutral molecule and the pH of a solution of ethanol in water is nearly 7.00. Ethanol can be quantitatively converted to its conjugate base, the ethoxide ion (CH₃CH₂O⁻), by reaction with an alkali metal such as sodium:

2 CH₃CH₂OH + 2 Na → 2 CH₃CH₂ONa + H₂

or a very strong base such as sodium hydride:

CH₃CH₂OH + NaH → CH₃CH₂ONa + H₂

The acidity of water and ethanol are nearly the same, as indicated by their pKa of 15.7 and 16 respectively. Thus, sodium ethoxide and sodium hydroxide exist in an equilbrium that is closely balanced:

CH₃CH₂OH + NaOH CH₃CH₂ONa + H₂O

Halogenation

Ethanol is not used industrially as a precursor to ethyl halides, but the reactions are illustrative. Ethanol reacts with hydrogen halides to produce ethyl halides such as ethyl chloride and ethyl bromide via an S_N2 reaction:

CH₃CH₂OH + HCl → CH₃CH₂Cl + H₂O

These reactions require a catalyst such as zinc chloride. HBr requires refluxing with a sulfuric acid catalyst. Ethyl halides can, in principle, also be produced by treating ethanol with more specialized halogenating agents, such as thionyl chloride or phosphorus tribromide.

CH₃CH₂OH + SOCl₂ → CH₃CH₂Cl + SO₂ + HCl

Upon treatment with halogens in the presence of base, ethanol gives the corresponding haloform (CHX₃, where X = Cl, Br, I). This conversion is called the haloform reaction. " An intermediate in the reaction with chlorine is the aldehyde called chloral:

4 Cl₂ + CH₃CH₂OH → CCl₃CHO + 5 HCl

Oxidation

Ethanol can be oxidized to acetaldehyde and further oxidized to acetic acid, depending on the reagents and conditions. This oxidation is of no importance industrially, but in the human body, these oxidation reactions are catalyzed by the enzyme liver alcohol dehydrogenase. The oxidation product of ethanol, acetic acid, is a nutrient for humans, being a precursor to acetyl CoA, where the acetyl group can be spent as energy or used for biosynthesis.

Other uses

Motor fuel

Energy content of some fuels compared with ethanol:
Fuel type	MJ/L	MJ/kg	Research octane number
Dry wood (20% moisture)		~19.5
Methanol	17.9	19.9	108.7
Ethanol	21.2	26.8	108.6
E85 (85% ethanol, 15% gasoline)	25.2	33.2	105
Liquefied natural gas	25.3	~55
Autogas (LPG) (60% propane + 40% butane)	26.8	50.
Aviation gasoline (high-octane gasoline, not jet fuel)	33.5	46.8	100/130 (lean/rich)
Gasohol (90% gasoline + 10% ethanol)	33.7	47.1	93/94
Regular gasoline/petrol	34.8	44.4	min. 91
Premium gasoline/petrol			max. 104
Diesel	38.6	45.4	25
Charcoal, extruded	50	23

Main article: Ethanol fuel

The largest single use of ethanol is as a motor fuel and fuel additive. More than any other major country, Brazil relies on ethanol as a motor fuel. Gasoline sold in Brazil contains at least 25% anhydrous ethanol. Hydrous ethanol (about 95% ethanol and 5% water) can be used as fuel in more than 90% of new cars sold in the country. Brazilian ethanol is produced from sugar cane and noted for high carbon sequestration. The US uses Gasohol (max 10% ethanol) and E85 (85% ethanol) ethanol/gasoline mixtures.
Ethanol may also be utilized as a rocket fuel, and is currently in lightweight rocket-powered racing aircraft.
Australian law limits the use of pure ethanol sourced from sugarcane waste to up to 10% in automobiles. It has been recommended that older cars (and vintage cars designed to use a slower burning fuel) have their valves upgraded or replaced.
According to an industry advocacy group for promoting ethanol called the American Coalition for Ethanol, ethanol as a fuel reduces harmful tailpipe emissions of carbon monoxide, particulate matter, oxides of nitrogen, and other ozone-forming pollutants. Argonne National Laboratory analyzed the greenhouse gas emissions of many different engine and fuel combinations. Comparing ethanol blends with gasoline alone, they showed reductions of 8% with the biodiesel/petrodiesel blend known as B20, 17% with the conventional E85 ethanol blend, and that using cellulosic ethanol lowers emissions 64%.
Ethanol combustion in an internal combustion engine yields many of the products of incomplete combustion produced by gasoline and significantly larger amounts of formaldehyde and related species such as acetaldehyde. This leads to a significantly larger photochemical reactivity that generates much more ground level ozone. These data have been assembled into The Clean Fuels Report comparison of fuel emissions and show that ethanol exhaust generates 2.14 times as much ozone as does gasoline exhaust. When this is added into the custom Localised Pollution Index (LPI) of The Clean Fuels Report the local pollution (pollution that contributes to smog) is 1.7 on a scale where gasoline is 1.0 and higher numbers signify greater pollution. The California Air Resources Board formalized this issue in 2008 by recognizing control standards for formaldehydes as an emissions control group, much like the conventional NOx and Reactive Organic Gases (ROGs).
World production of ethanol in 2006 was 51 gigalitres (1.3×10¹⁰ US gal), with 69% of the world supply coming from Brazil and the United States. More than 20% of Brazilian cars are able to use 100% ethanol as fuel, which includes ethanol-only engines and flex-fuel engines. Flex-fuel engines in Brazil are able to work with all ethanol, all gasoline or any mixture of both. In the US flex-fuel vehicles can run on 0% to 85% ethanol (15% gasoline) since higher ethanol blends are not yet allowed or efficient. Brazil supports this population of ethanol-burning automobiles with large national infrastructure that produces ethanol from domestically grown sugar cane. Sugar cane not only has a greater concentration of sucrose than corn (by about 30%), but is also much easier to extract. The bagasse generated by the process is not wasted, but is used in power plants to produce electricity.
The United States fuel ethanol industry is based largely on corn. According to the Renewable Fuels Association, as of October 30, 2007, 131 grain ethanol bio-refineries in the United States have the capacity to produce 7.0 billion US gallons (26,000,000 m³) of ethanol per year. An additional 72 construction projects underway (in the U.S.) can add 6.4 billion US gallons (24,000,000 m³) of new capacity in the next 18 months. Over time, it is believed that a material portion of the ≈150-billion-US-gallon (570,000,000 m³) per year market for gasoline will begin to be replaced with fuel ethanol.
Sweet sorghum is a potential source of ethanol, which is suitable for growing in dryland conditions. It is being investigated by the International Crops Research Institute for the Semi-Arid Tropics (ICRISAT) for its potential to provide fuel, along with food and animal feed, in arid parts of Asia and Africa. The water requirement of sweet sorghum is one-third that of sugarcane on a comparable time scale. Also, sweet sorghum requires about 22% less water than corn also known as maize. The world’s first sweet sorghum-based ethanol production distillery began commercial ethanol production in 2007 in Andhra Pradesh, India.
Ethanol's high miscibility with water means that it cannot be shipped through modern pipelines like liquid hydrocarbons. Mechanics have seen increased cases of damage to small engines, in particular, the carburetor, attributable to the increased water retention by ethanol in fuel.

Household heating

Ethanol fuels flue-less, real flame fireplaces. Ethanol is kept in a burner containing a wick such as glass wool, a safety shield to reduce the chances of accidents and an extinguisher such as a plate or shutter to cut off oxygen.
It provides almost the same visual benefits of a real flame log or coal fire without the need to vent the fumes via a flue as ethanol produces very little hazardous carbon monoxide, and little or no noticeable scent. It does emit carbon dioxide and requires oxygen. Therefore, external ventilation of the room containing the fire is needed to ensure safe operation.
An additional benefit is that, unlike a flue based fireplace, 100% of the heat energy produced enters the room. This serves to offset some of the heat loss from an external air vent, as well as offset the relatively high cost of the fuel compared to other forms of heating.

Feedstock

Main article: § Reactions

Ethanol is an important industrial ingredient and has widespread use as a base chemical for other organic compounds. These include ethyl halides, ethyl esters, diethyl ether, acetic acid, ethyl amines, and, to a lesser extent, butadiene.

Antiseptic

Ethanol is used in medical wipes and in most common antibacterial hand sanitizer gels at a concentration of about 62% v/v as an antiseptic. Ethanol kills organisms by denaturing their proteins and dissolving their lipids and is effective against most bacteria and fungi, and many viruses, but is ineffective against bacterial spores.

Solvent

Ethanol is miscible with water and is a good general purpose solvent. It is found in paints, tinctures, markers, and personal care products such as perfumes and deodorants.

                          NATURAL GAS

Natural gas is a fossil fuel formed when layers of buried plants, gases, and animals are exposed to intense heat and pressure over thousands of years. The energy that the plants originally obtained from the sun is stored in the form of chemical bonds in natural gas. Natural gas is a nonrenewable resource because it cannot be replenished on a human time frame. Natural gas is a hydrocarbon gas mixture consisting primarily of methane, but commonly includes varying amounts of other higher alkanes and even a lesser percentage of carbon dioxide, nitrogen, and hydrogen sulfide. Natural gas is an energy source often used for heating, cooking, and electricity generation. It is also used as fuel for vehicles and as a chemical feedstock in the manufacture of plastics and other commercially important organic chemicals.
Natural gas is found in deep underground rock formations or associated with other hydrocarbon reservoirs in coal beds and as methane clathrates. Petroleum is another resource and fossil fuel found in close proximity to, and with natural gas. Most natural gas was created over time by two mechanisms: biogenic and thermogenic. Biogenic gas is created by methanogenic organisms in marshes, bogs, landfills, and shallow sediments. Deeper in the earth, at greater temperature and pressure, thermogenic gas is created from buried organic material.
Before natural gas can be used as a fuel, it must be processed to remove impurities, including water, to meet the specifications of marketable natural gas. The by-products of this processing include ethane, propane, butanes, pentanes, and higher molecular weight hydrocarbons, hydrogen sulfide (which may be converted into pure sulfur), carbon dioxide, water vapor, and sometimes helium and nitrogen.
Natural gas is often informally referred to simply as "gas", especially when compared to other energy sources such as oil or coal. However, it is not to be confused with gasoline, especially in North America, where the term gasoline is often shortened in colloquial usage to gas.
Natural gas was used by the Chinese in about 500 BC. They discovered a way to transport gas seeping from the ground in crude pipelines of bamboo to where it was used to boil sea water to extract the salt. The world's first industrial extraction of natural gas started at Fredonia, New York, USA in 1825. By 2009, 66 trillion cubic meters (or 8%) had been used out of the total 850 trillion cubic meters of estimated remaining recoverable reserves of natural gas. Based on an estimated 2015 world consumption rate of about 3.4 trillion cubic meters of gas per year, the total estimated remaining economically recoverable reserves of natural gas would last 250 years at current consumption rates. An annual increase in usage of 2-3% could result in currently recoverable reserves lasting significantly less, perhaps as few as 80 to 100 years.

Natural gas

Trends in the top five natural gas-producing countries (US EIA data)

In the 19th century, natural gas was usually obtained as a by-product of producing oil, since the small, light gas carbon chains came out of solution as the extracted fluids underwent pressure reduction from the reservoir to the surface, similar to uncapping a bottle of soda where the carbon dioxide effervesces. Unwanted natural gas was a disposal problem in the active oil fields. If there was not a market for natural gas near the wellhead it was virtually valueless since it had to be piped to the end user.

In the 19th century and early 20th century, such unwanted gas was usually burned off at oil fields. Today, unwanted gas (or stranded gas without a market) associated with oil extraction often is returned to the reservoir with 'injection' wells while awaiting a possible future market or to repressurize the formation, which can enhance extraction rates from other wells. In regions with a high natural gas demand (such as the US), pipelines are constructed when it is economically feasible to transport gas from a wellsite to an end consumer.

In addition to transporting gas via pipelines for use in power generation, other end uses for natural gas include export as liquefied natural gas (LNG) or conversion of natural gas into other liquid products via gas-to-liquids (GTL) technologies. GTL technologies can convert natural gas into liquids products such as gasoline, diesel or jet fuel. A variety of GTL technologies have been developed, including Fischer-Tropsch (F-T), methanol to gasoline (MTG) and STG+. F-T produces a synthetic crude that can be further refined into finished products, while MTG can produce synthetic gasoline from natural gas. STG+ can produce drop-in gasoline, diesel, jet fuel and aromatic chemicals directly from natural gas via a single-loop process. In 2011, Royal Dutch Shell’s 140,000 barrel per day F-T plant went into operation in Qatar.

Natural gas can be "associated" (found in oil fields), or "non-associated" (isolated in natural gas fields), and is also found in coal beds (as coalbed methane). It sometimes contains a significant amount of ethane, propane, butane, and pentane—heavier hydrocarbons removed for commercial use prior to the methane being sold as a consumer fuel or chemical plant feedstock. Non-hydrocarbons such as carbon dioxide, nitrogen, helium (rarely), and hydrogen sulfide must also be removed before the natural gas can be transported.

Natural gas extracted from oil wells is called casinghead gas or associated gas. The natural gas industry is extracting an increasing quantity of gas from challenging resource types: sour gas, tight gas, shale gas, and coalbed methane.

There is some disagreement on which country has the largest proven gas reserves. Sources that consider that Russia has by far the largest proven reserves include the US CIA (47.6 trillion cubic meters), the US Energy Information Administration (47.8 tcm), and OPEC (48.7 tcm). However, BP credits Russia with only 32.9 tcm, which would place it in second place, slightly behind Iran (33.1 to 33.8 tcm, depending on the source). With Gazprom, Russia is frequently the world's largest natural gas extractor. Major proven resources (in billion cubic meters) are world 187,300 (2013), Iran 33,600 (2013), Russia 32,900 (2013), Qatar 25,100 (2013), Turkmenistan 17,500 (2013) and the United States 8,500 (2013).

It is estimated that there are about 900 trillion cubic meters of "unconventional" gas such as shale gas, of which 180 trillion may be recoverable. In turn, many studies from MIT, Black & Veatch and the DOE predict that natural gas will account for a larger portion of electricity generation and heat in the future.

The world's largest gas field is the offshore South Pars / North Dome Gas-Condensate field, shared between Iran and Qatar. It is estimated to have 51 trillion cubic meters of natural gas and 50 billion barrels of natural gas condensates.

Because natural gas is not a pure product, as the reservoir pressure drops when non-associated gas is extracted from a field under supercritical (pressure/temperature) conditions, the higher molecular weight components may partially condense upon isothermic depressurizing—an effect called retrograde condensation. The liquid thus formed may get trapped as the pores of the gas reservoir get depleted. One method to deal with this problem is to re-inject dried gas free of condensate to maintain the underground pressure and to allow re-evaporation and extraction of condensates. More frequently, the liquid condenses at the surface, and one of the tasks of the gas plant is to collect this condensate. The resulting liquid is called natural gas liquid (NGL) and has commercial value.

Shale gas

The examples and perspective in this article deal primarily with the United States and do not represent a worldwide view of the subject. Please improve this article and discuss the issue on the talk page. (September 2013)

The location of shale gas compared to other types of gas deposits.

Main article: Shale gas

Shale gas is natural gas produced from shale. Because shale has matrix permeability too low to allow gas to flow in economical quantities, shale gas wells depend on fractures to allow the gas to flow. Early shale gas wells depended on natural fractures through which gas flowed; almost all shale gas wells today require fractures artificially created by hydraulic fracturing. Since 2000, shale gas has become a major source of natural gas in the United States and Canada. Following the success in the United States, shale gas exploration is beginning in countries such as Poland, China, and South Africa.

Town gas

Main article: History of manufactured gas

Town gas is a flammable gaseous fuel made by the destructive distillation of coal and contains a variety of calorific gases including hydrogen, carbon monoxide, methane, and other volatile hydrocarbons, together with small quantities of non-calorific gases such as carbon dioxide and nitrogen, and is used in a similar way to natural gas. This is a historical technology, not usually economically competitive with other sources of fuel gas today. But there are still some specific cases where it is the best option and it may be so into the future.

Most town "gashouses" located in the eastern US in the late 19th and early 20th centuries were simple by-product coke ovens that heated bituminous coal in air-tight chambers. The gas driven off from the coal was collected and distributed through networks of pipes to residences and other buildings where it was used for cooking and lighting. (Gas heating did not come into widespread use until the last half of the 20th century.) The coal tar (or asphalt) that collected in the bottoms of the gashouse ovens was often used for roofing and other waterproofing purposes, and when mixed with sand and gravel was used for paving streets.

Biogas

Main article: Biogas

Methanogenic archaea are responsible for all biological sources of methane. Some live in symbiotic relationships with other life forms, including termites, ruminants, and cultivated crops. Other sources of methane, the principal component of natural gas, include landfill gas, biogas, and methane hydrate. When methane-rich gases are produced by the anaerobic decay of non-fossil organic matter (biomass), these are referred to as biogas (or natural biogas). Sources of biogas include swamps, marshes, and landfills (see landfill gas), as well as agricultural waste materials such as sewage sludge and manure by way of anaerobic digesters, in addition to enteric fermentation, particularly in cattle. Landfill gas is created by decomposition of waste in landfill sites. Excluding water vapor, about half of landfill gas is methane and most of the rest is carbon dioxide, with small amounts of nitrogen, oxygen, and hydrogen, and variable trace amounts of hydrogen sulfide and siloxanes. If the gas is not removed, the pressure may get so high that it works its way to the surface, causing damage to the landfill structure, unpleasant odor, vegetation die-off, and an explosion hazard. The gas can be vented to the atmosphere, flared or burned to produce electricity or heat. Biogas can also be produced by separating organic materials from waste that otherwise goes to landfills. This method is more efficient than just capturing the landfill gas it produces. Anaerobic lagoons produce biogas from manure, while biogas reactors can be used for manure or plant parts. Like landfill gas, biogas is mostly methane and carbon dioxide, with small amounts of nitrogen, oxygen and hydrogen. However, with the exception of pesticides, there are usually lower levels of contaminants.

Landfill gas cannot be distributed through utility natural gas pipelines unless it is cleaned up to less than 3 per cent CO2, and a few parts per million H2S, because CO2 and H2S corrode the pipelines. The presence of CO2 will lower the energy level of the gas below requirements for the pipeline. Siloxanes in the gas will form deposits in gas burners and need to be removed prior to entry into any gas distribution or transmission system. Consequently it may be more economical to burn the gas on site or within a short distance of the landfill using a dedicated pipeline. Water vapor is often removed, even if the gas is burned on site. If low temperatures condense water out of the gas, siloxanes can be lowered as well because they tend to condense out with the water vapor. Other non-methane components may also be removed to meet emission standards, to prevent fouling of the equipment or for environmental considerations. Co-firing landfill gas with natural gas improves combustion, which lowers emissions.

Biogas, and especially landfill gas, are already used in some areas, but their use could be greatly expanded. Experimental systems were being proposed for use in parts of Hertfordshire, UK, and Lyon in France. Using materials that would otherwise generate no income, or even cost money to get rid of, improves the profitability and energy balance of biogas production. Gas generated in sewage treatment plants is commonly used to generate electricity. For example, the Hyperion sewage plant in Los Angeles burns 8 million cubic feet (230,000 m³) of gas per day to generate power New York City utilizes gas to run equipment in the sewage plants, to generate electricity, and in boilers. Using sewage gas to make electricity is not limited to large cities. The city of Bakersfield, California, uses cogeneration at its sewer plants. California has 242 sewage wastewater treatment plants, 74 of which have installed anaerobic digesters. The total biopower generation from the 74 plants is about 66 MW.

The McMahon natural gas processing plant in Taylor, British Columbia, Canada.

Crystallized natural gas — hydrates

Huge quantities of natural gas (primarily methane) exist in the form of hydrates under sediment on offshore continental shelves and on land in arctic regions that experience permafrost, such as those in Siberia. Hydrates require a combination of high pressure and low temperature to form.

In 2010, the cost of extracting natural gas from crystallized natural gas was estimated to 100–200 per cent the cost of extracting natural gas from conventional sources, and even higher from offshore deposits.

In 2013, Japan Oil, Gas and Metals National Corporation (JOGMEC) announced that they had recovered commercially relevant quantities of natural gas from methane hydrate.

Natural gas processing

Main article: Natural gas processing

The image below is a schematic block flow diagram of a typical natural gas processing plant. It shows the various unit processes used to convert raw natural gas into sales gas pipelined to the end user markets.

The block flow diagram also shows how processing of the raw natural gas yields byproduct sulfur, byproduct ethane, and natural gas liquids (NGL) propane, butanes and natural gasoline (denoted as pentanes +).

Schematic flow diagram of a typical natural gas processing plant.

Depletion

Main article: Gas depletion

Uses

Mid Stream Natural Gas

Natural gas flowing in the distribution lines and at the natural gas well head are often used to power natural gas powered engines. These engines rotate compressors to facilitate the natural gas transmission. These compressors are required in the mid-stream line to pressurize and to re-pressurize the natural gas in the transmission line as the gas travels. The natural gas transmission lines extend to the natural gas processing plant or unit which removes the higher molecular weighted natural gas hydrocarbons to produce a British thermal unit (BTU) value between 950 and 1050 BTU's. The processed natural gas may then be used for residential, commercial and industrial uses.

Often mid-stream and well head gases require removal of many of the various hydrocarbon species contained within the natural gas. Some of these gases include heptane, pentane, propane and other hydrocarbons with molecular weights above Methane (CH4) to produce a natural gas fuel which is used to operate the natural gas engines for further pressurized transmission. Typically, natural gas compressors require 950 to 1050 BTU per cubic foot to operate at the natural gas engines rotational name plate specifications.

Several methods are used to remove these higher molecular weighted gases for use at the natural gas engine. A few technologies are as follows:

• Joule–Thomson Skid
• Cryogenic or Chiller System
• Chemical Enzymology System

Power generation

Natural gas is a major source of electricity generation through the use of cogeneration, gas turbines and steam turbines. Natural gas is also well suited for a combined use in association with renewable energy sources such as wind or solar and for alimenting peak-load power stations functioning in tandem with hydroelectric plants. Most grid peaking power plants and some off-grid engine-generators use natural gas. Particularly high efficiencies can be achieved through combining gas turbines with a steam turbine in combined cycle mode. Natural gas burns more cleanly than other hydrocarbon fuels, such as oil and coal, and produces less carbon dioxide per unit of energy released. For an equivalent amount of heat, burning natural gas produces about 30 per cent less carbon dioxide than burning petroleum and about 45 per cent less than burning coal.

Coal-fired electric power generation emits around 2,000 pounds of carbon dioxide for every megawatt hour generated, which is almost double the carbon dioxide released by a natural gas-fired electric plant per megawatt hour generated. Because of this higher carbon efficiency of natural gas generation, as the fuel mix in the United States has changed to reduce coal and increase natural gas generation, carbon dioxide emissions have unexpectedly fallen. Those measured in the first quarter of 2012 were the lowest of any recorded for the first quarter of any year since 1992.

Combined cycle power generation using natural gas is currently the cleanest available source of power using hydrocarbon fuels, and this technology is widely and increasingly used as natural gas can be obtained at increasingly reasonable costs. Fuel cell technology may eventually provide cleaner options for converting natural gas into electricity, but as yet it is not price-competitive. Locally produced electricity and heat using natural gas powered Combined Heat and Power plant (CHP or Cogeneration plant) is considered energy efficient and a rapid way to cut carbon emissions.

Domestic use

Natural gas dispensed from a simple stovetop can generate temperatures in excess of 1100 °C (2000 °F) making it a powerful domestic cooking and heating fuel. In much of the developed world it is supplied through pipes to homes, where it is used for many purposes including ranges and ovens, gas-heated clothes dryers, heating/cooling, and central heating. Heaters in homes and other buildings may include boilers, furnaces, and water heaters.

Compressed natural gas (CNG) is used in rural homes without connections to piped-in public utility services, or with portable grills. Natural gas is also supplied by independent natural gas suppliers through Natural Gas Choice programs throughout the United States. However, as CNG costs more than LPG, LPG (propane) is the dominant source of rural gas. A Washington, D.C. Metrobus, which runs on natural gas.

Transportation

CNG is a cleaner alternative to other automobile fuels such as gasoline (petrol) and diesel. By the end of 2012 there were 17.25 million natural gas vehicles worldwide, led by Iran (3.3 million), Pakistan (3.1 million), Argentina (2.18 million), Brazil (1.73 million), India (1.5 million), and China (1.5 million). The energy efficiency is generally equal to that of gasoline engines, but lower compared with modern diesel engines. Gasoline/petrol vehicles converted to run on natural gas suffer because of the low compression ratio of their engines, resulting in a cropping of delivered power while running on natural gas (10%–15%). CNG-specific engines, however, use a higher compression ratio due to this fuel's higher octane number of 120–130.

Fertilizers

Natural gas is a major feedstock for the production of ammonia, via the Haber process, for use in fertilizer production.

Aviation

Russian aircraft manufacturer Tupolev is currently running a development program to produce LNG- and hydrogen-powered aircraft. The program has been running since the mid-1970s, and seeks to develop LNG and hydrogen variants of the Tu-204 and Tu-334 passenger aircraft, and also the Tu-330 cargo aircraft. It claims that at current market prices, an LNG-powered aircraft would cost 5,000 roubles (~ $218/ £112) less to operate per ton, roughly equivalent to 60 per cent, with considerable reductions to carbon monoxide, hydrocarbon and nitrogen oxide emissions.

The advantages of liquid methane as a jet engine fuel are that it has more specific energy than the standard kerosene mixes do and that its low temperature can help cool the air which the engine compresses for greater volumetric efficiency, in effect replacing an intercooler. Alternatively, it can be used to lower the temperature of the exhaust.

Hydrogen

Natural gas can be used to produce hydrogen, with one common method being the hydrogen reformer. Hydrogen has many applications: it is a primary feedstock for the chemical industry, a hydrogenating agent, an important commodity for oil refineries, and the fuel source in hydrogen vehicles.

Other

Natural gas is also used in the manufacture of fabrics, glass, steel, plastics, paint, and other products.

Storage and transport

Because of its low density, it is not easy to store natural gas or to transport it by vehicle. Natural gas pipelines are impractical across oceans. Many existing pipelines in America are close to reaching their capacity, prompting some politicians representing northern states to speak of potential shortages. In Western Europe, the gas pipeline network is already dense. New pipelines are planned or under construction in Eastern Europe and between gas fields in Russia, Near East and Northern Africa and Western Europe. See also List of natural gas pipelines.

LNG carriers transport liquefied natural gas (LNG) across oceans, while tank trucks can carry liquefied or compressed natural gas (CNG) over shorter distances. Sea transport using CNG carrier ships that are now under development may be competitive with LNG transport in specific conditions.

Gas is turned into liquid at a liquefaction plant, and is returned to gas form at regasification plant at the terminal. Shipborne regasification equipment is also used. LNG is the preferred form for long distance, high volume transportation of natural gas, whereas pipeline is preferred for transport for distances up to 4,000 km (2,485 mi) over land and approximately half that distance offshore.

CNG is transported at high pressure, typically above 200 bars. Compressors and decompression equipment are less capital intensive and may be economical in smaller unit sizes than liquefaction/regasification plants. Natural gas trucks and carriers may transport natural gas directly to end-users, or to distribution points such as pipelines.

Peoples Gas Manlove Field natural gas storage area in Newcomb Township, Champaign County, Illinois. In the foreground (left) is one of the numerous wells for the underground storage area, with an LNG plant, and above ground storage tanks are in the background (right).

In the past, the natural gas which was recovered in the course of recovering petroleum could not be profitably sold, and was simply burned at the oil field in a process known as flaring. Flaring is now illegal in many countries. Additionally, higher demand in the last 20–30 years has made production of gas associated with oil economically viable. A further option is the gas is now sometimes re-injected into the formation for enhanced oil recovery by pressure maintenance as well as miscible or immiscible flooding. Conservation, re-injection, or flaring of natural gas associated with oil is primarily dependent on proximity to markets (pipelines), and regulatory restrictions.

A "master gas system" was invented in Saudi Arabia in the late 1970s, ending any necessity for flaring. Satellite observation, however, shows that flaring and venting are still practiced in some gas-extracting countries.

Natural gas is used to generate electricity and heat for desalination. Similarly, some landfills that also discharge methane gases have been set up to capture the methane and generate electricity.

Natural gas is often stored underground inside depleted gas reservoirs from previous gas wells, salt domes, or in tanks as liquefied natural gas. The gas is injected in a time of low demand and extracted when demand picks up. Storage nearby end users helps to meet volatile demands, but such storage may not always be practicable.

With 15 countries accounting for 84 per cent of the worldwide extraction, access to natural gas has become an important issue in international politics, and countries vie for control of pipelines. In the first decade of the 21st century, Gazprom, the state-owned energy company in Russia, engaged in disputes with Ukraine and Belarus over the price of natural gas, which have created concerns that gas deliveries to parts of Europe could be cut off for political reasons. The United States is preparing to export natural gas.

Floating Liquefied Natural Gas (FLNG) is an innovative technology designed to enable the development of offshore gas resources that would otherwise remain untapped because due to environmental or economic factors it is nonviable to develop them via a land-based LNG operation. FLNG technology also provides a number of environmental and economic advantages:

• Environmental – Because all processing is done at the gas field, there is no requirement for long pipelines to shore, compression units to pump the gas to shore, dredging and jetty construction, and onshore construction of an LNG processing plant, which significantly reduces the environmental footprint. Avoiding construction also helps preserve marine and coastal environments. In addition, environmental disturbance will be minimised during decommissioning because the facility can easily be disconnected and removed before being refurbished and re-deployed elsewhere.

• Economic – Where pumping gas to shore can be prohibitively expensive, FLNG makes development economically viable. As a result, it will open up new business opportunities for countries to develop offshore gas fields that would otherwise remain stranded, such as those offshore East Africa.

Many gas and oil companies are considering the economic and environmental benefits of Floating Liquefied Natural Gas (FLNG). However, for the time being, the only FLNG facility now in development is being built by Shell, due for completion around 2017.

Environmental effects

Effect of natural gas release

Natural gas is mainly composed of methane. After release to the atmosphere it is removed over about 10 years by gradual oxidation to carbon dioxide and water by hydroxyl radicals (·OH) formed in the troposphere or stratosphere, giving the overall chemical reaction CH₄ + 2O₂→ CO₂ + 2H₂O. While the lifetime of atmospheric methane is relatively short when compared to carbon dioxide, it is more efficient at trapping heat in the atmosphere, so that a given quantity of methane has 84 times the global-warming potential of carbon dioxide over a 20-year period and 28 times over a 100-year period. Natural gas is thus a more potent greenhouse gas than carbon dioxide due to the greater global-warming potential of methane. Current estimates by the EPA place global emissions of methane at 85 billion cubic metres (3.0×10¹² cu ft) annually, or 3.2 per cent of global production. Direct emissions of methane represented 14.3 per cent of all global anthropogenic greenhouse gas emissions in 2004.

During extraction, storage, transportation, and distribution, natural gas is known to leak into the atmosphere, particularly during the extraction process. A Cornell University study in 2011 demonstrated that the leak rate of methane may be high enough to jeopardize its global warming advantage over coal. This study was criticized later for its high assumption of methane leakage values. These values were later shown to be close to the findings of the Scientists at the National Oceanic and Atmospheric Administration. Natural gas extraction also releases an isotope of Radon, ranging from 5 to 200,000 Becquerels per cubic meter.

CO₂ emissions

Natural gas is often described as the cleanest fossil fuel. It produces about 29% and 44% less carbon dioxide per joule delivered than oil and coal respectively, and potentially fewer pollutants than other hydrocarbon fuels. However, in absolute terms, it comprises a substantial percentage of human carbon emissions, and this contribution is projected to grow. According to the IPCC Fourth Assessment Report, in 2004, natural gas produced about 5.3 billion tons a year of CO₂ emissions, while coal and oil produced 10.6 and 10.2 billion tons respectively. According to an updated version of the Special Report on Emissions Scenario by 2030, natural gas would be the source of 11 billion tons a year, with coal and oil now 8.4 and 17.2 billion respectively because demand is increasing 1.9 percent a year. Total global emissions for 2004 were estimated at over 27,200 million tons.

Other pollutants

Natural gas produces far lower amounts of sulfur dioxide and nitrous oxides than any other hydrocarbon fuels. The other pollutants due to natural gas combustion are listed below in parts per million (ppm):

• Carbon monoxide - 40 ppm
• Sulfur dioxide - 1 ppm
• Nitrogen oxide - 92 ppm
• Particulates - 7 ppm

Safety concern

Production

In mines, where methane seeping from rock formations has no odor, sensors are used, and mining apparatus such as the Davy lamp has been specifically developed to avoid ignition sources.

Some gas fields yield sour gas containing hydrogen sulfide (H₂S). This untreated gas is toxic. Amine gas treating, an industrial scale process which removes acidic gaseous components, is often used to remove hydrogen sulfide from natural gas.

Extraction of natural gas (or oil) leads to decrease in pressure in the reservoir. Such decrease in pressure in turn may result in subsidence, sinking of the ground above. Subsidence may affect ecosystems, waterways, sewer and water supply systems, foundations, and so on.

Another ecosystem effect results from the noise of the process. This can change the composition of animal life in the area, and have consequences for plants as well in that animals disperse seeds and pollen.

Releasing the gas from low-permeability reservoirs is accomplished by a process called hydraulic fracturing or "hydrofracking". To allow the natural gas to flow out of the shale, oil operators force 1 to 9 million US gallons (34,000 m³) of water mixed with a variety of chemicals through the wellbore casing into the shale. The high pressure water breaks up or "fracks" the shale, which releases the trapped gas. Sand is added to the water as a proppant to keep the fractures in the shale open, thus enabling the gas to flow into the casing and then to the surface. The chemicals are added to the frack fluid to reduce friction and combat corrosion. During the extracting life of a gas well, other low concentrations of other chemical substances may be used, such as biocides to eliminate fouling, scale and corrosion inhibitors, oxygen scavengers to remove a source of corrosion, and acids to clean the perforations in the pipe.

Dealing with fracking fluid can be a challenge. Along with the gas, 30 per cent to 70 per cent of the chemically laced frack fluid, or flow back, returns to the surface. Additionally, a significant amount of brine, containing salt and other minerals, may be produced with the gas.

Use

In order to assist in detecting leaks, a minute amount of odorant is added to the otherwise colorless and almost odorless gas used by consumers. The odor has been compared to the smell of rotten eggs, due to the added tert-Butylthiol (t-butyl mercaptan). Sometimes a related compound, thiophane, may be used in the mixture. Situations in which an odorant that is added to natural gas can be detected by analytical instrumentation, but cannot be properly detected by an observer with a normal sense of smell, have occurred in the natural gas industry. This is caused by odor masking, when one odorant overpowers the sensation of another. As of 2011, the industry is conducting research on the causes of odor masking.

Explosions caused by natural gas leaks occur a few times each year. Individual homes, small businesses and other structures are most frequently affected when an internal leak builds up gas inside the structure. Frequently, the blast is powerful enough to significantly damage a building but leave it standing. In these cases, the people inside tend to have minor to moderate injuries. Occasionally, the gas can collect in high enough quantities to cause a deadly explosion, disintegrating one or more buildings in the process. The gas usually dissipates readily outdoors, but can sometimes collect in dangerous quantities if flow rates are high enough. However, considering the tens of millions of structures that use the fuel, the individual risk of using natural gas is very low.

Natural gas heating systems are a minor source of carbon monoxide deaths in the United States. According to the US Consumer Product Safety Commission (2008), 56 per cent of unintentional deaths from non-fire CO poisoning were associated with engine-driven tools like gas-powered generators and lawnmowers. Natural gas heating systems accounted for 4 per cent of these deaths. Improvements in natural gas furnace designs have greatly reduced CO poisoning concerns. Detectors are also available that warn of carbon monoxide and/or explosive gas (methane, propane, etc.).

Energy content, statistics, and pricing

Main article: Natural gas prices

Quantities of natural gas are measured in normal cubic meters (corresponding to 0 °C at 101.325 kPa) or in standard cubic feet (corresponding to 60 °F (16 °C) and 14.73 psia). The gross heat of combustion of 1 m³ of commercial quality natural gas is around 39 MJ (≈10.8 kWh), but this can vary by several percent. This comes to about 49 MJ (≈13.5 kWh) for 1 kg of natural gas (assuming a density of 0.8 kg m⁻³, an approximate value).

The price of natural gas varies greatly depending on location and type of consumer. In 2007, a price of $7 per 1000 cubic feet (about 25 cents per m³) was typical in the United States. The typical caloric value of natural gas is roughly 1,000 British thermal units (BTU) per cubic foot, depending on gas composition. This corresponds to around $7 per million BTU, or around $7 per gigajoule. In April 2008, the wholesale price was $10 per 1,000 cubic feet (28 m³) ($10/MMBTU). The residential price varies from 50% to 300% more than the wholesale price. At the end of 2007, this was $12–$16 per 1000 cubic feet (about 50 cents per m³). Natural gas in the United States is traded as a futures contract on the New York Mercantile Exchange. Each contract is for 10,000 MMBTU (~10,550 gigajoules), or 10 billion BTU. Thus, if the price of gas is $10 per million BTUs on the NYMEX, the contract is worth $100,000.

European Union

Gas prices for end users vary greatly across the EU. A single European energy market, one of the key objectives of the European Union, should level the prices of gas in all EU member states. Moreover, it would help to resolve supply and global warming issues.

United States

U.S. Natural Gas Marketed Production 1900 to 2012, source US EIA

In US units, one standard cubic foot 1 cubic foot (28 L) of natural gas produces around 1,028 British thermal units (1,085 kJ). The actual heating value when the water formed does not condense is the net heat of combustion and can be as much as 10% less.

In the United States, retail sales are often in units of therms (th); 1 therm = 100,000 BTU. Gas meters measure the volume of gas used, and this is converted to therms by multiplying the volume by the energy content of the gas used during that period, which varies slightly over time. Wholesale transactions are generally done in decatherms (Dth), or in thousand decatherms (MDth), or in million decatherms (MMDth). A million decatherms is roughly a billion cubic feet of natural gas. Gas sales to domestic consumers may be in units of 100 standard cubic feet (scf). The typical annual consumption of a single family residence is 1,000 therms or one RCE.

Canada

Canada uses metric measure for internal trade of petrochemical products. Consequently, natural gas is sold by the Gigajoule, cubic metre (m³) or thousand cubic metres (E3m3). Distribution infrastructure and meters almost always meter volume (cubic foot or cubic meter). Some jurisdictions, such as Saskatchewan, sell gas by volume only. Other jurisdictions, such as Alberta, gas is sold by the energy content (GJ). In these areas, almost all meters for residential and small commercial customers measure volume (m³ or ft³), and billing statements include a multiplier to convert the volume to energy content of the local gas supply.

A Gigajoule (GJ) is a measure approximately equal to half a barrel (250 lbs) of oil, or 1 million BTUs, or 1000 cu ft of gas, or 28 m³ of gas. The energy content of gas supply in Canada can vary from 37 to 43 MJ per m³ depending on gas supply and processing between the wellhead and the customer.

Elsewhere

In the rest of the world, natural gas is sold in Gigajoule retail units. LNG (liquefied natural gas) and LPG (liquefied petroleum gas) are traded in metric tons or MMBTU as spot deliveries. Long term natural gas distribution contracts are signed in cubic metres, and LNG contracts are in metric tonnes (1,000 kg). The LNG and LPG is transported by specialized transport ships, as the gas is liquified at cryogenic temperatures. The specification of each LNG/LPG cargo will usually contain the energy content, but this information is in general not available to the public.

In the Russian Federation, Gazprom sold approximately 250 billion cubic metres of natural gas in 2008. In 2013 the Group produced 487.4 billion cubic meters of natural and associated gas. Gazprom supplied Europe with 161.5 billion cubic meters of gas in 2013.

Natural gas as an asset class for institutional investors

Research conducted by the World Pensions Council (WPC) suggests that large US and Canadian pension funds and Asian and MENA area SWF investors have become particularly active in the fields of natural gas and natural gas infrastructure, a trend started in 2005 by the formation of Scotia Gas Networks in the UK by OMERS and Ontario Teachers' Pension Plan.

Adsorbed Natural Gas (ANG)

Another way to store natural gas is adsorbing it to the porous solids called sorbents. The best condition for methane storage is at room temperature and atmospheric pressure. The used pressure can be up to 4 MPa (about 40 times atmospheric pressure) for having more storage capacity. The most common sorbent used for ANG is activated carbon (AC). Three main types of activated carbons for ANG are: Activated Carbon Fiber (ACF), Powdered Activated Carbon (PAC), activated carbon monolith.

 

            LIQUEFIED PETROLEUM GAS

Liquefied petroleum gas or liquid petroleum gas (LPG or LP gas), also referred to as simply propane or butane, is a flammable mixture of hydrocarbon gases used as a fuel in heating appliances, cooking equipment, and vehicles.
It is increasingly used as an aerosol propellant and a refrigerant, replacing chlorofluorocarbons in an effort to reduce damage to the ozone layer. When specifically used as a vehicle fuel it is often referred to as autogas.
Varieties of LPG bought and sold include mixes that are primarily propane (C3H8), primarily butane (C4H10) and, most commonly, mixes including both propane and butane. In winter, the mixes contain more propane, while in summer, they contain more butane. In the United States, primarily two grades of LPG are sold: commercial propane and HD-5. These specifications are published by the Gas Processors Association (GPA) and the American Society of Testing and Materials (ASTM). Propane/butane blends are also listed in these specifications.
Propylene, butylenes and various other hydrocarbons are usually also present in small concentrations. HD-5 limits the amount of propylene that can be placed in LPG to 5%, and is utilized as an autogas specification. A powerful odorant, ethanethiol, is added so that leaks can be detected easily. The international standard is EN 589. In the United States, tetrahydrothiophene (thiophane) or amyl mercaptan are also approved odorants, although neither is currently being utilized.
LPG is prepared by refining petroleum or "wet" natural gas, and is almost entirely derived from fossil fuel sources, being manufactured during the refining of petroleum (crude oil), or extracted from petroleum or natural gas streams as they emerge from the ground. It was first produced in 1910 by Dr. Walter Snelling, and the first commercial products appeared in 1912. It currently provides about 3% of all energy consumed, and burns relatively cleanly with no soot and very few sulfur emissions. As it is a gas, it does not pose ground or water pollution hazards, but it can cause air pollution. LPG has a typical specific calorific value of 46.1 MJ/kg compared with 42.5 MJ/kg for fuel oil and 43.5 MJ/kg for premium grade petrol (gasoline). However, its energy density per volume unit of 26 MJ/L is lower than either that of petrol or fuel oil, as its relative density is lower (about 0.5–0.58, compared to 0.71–0.77 for gasoline).
As its boiling point is below room temperature, LPG will evaporate quickly at normal temperatures and pressures and is usually supplied in pressurised steel vessels. They are typically filled to 80–85% of their capacity to allow for thermal expansion of the contained liquid. The ratio between the volumes of the vaporized gas and the liquefied gas varies depending on composition, pressure, and temperature, but is typically around 250:1. The pressure at which LPG becomes liquid, called its vapour pressure, likewise varies depending on composition and temperature; for example, it is approximately 220 kilopascals (32 psi) for pure butane at 20 °C (68 °F), and approximately 2,200 kilopascals (320 psi) for pure propane at 55 °C (131 °F). LPG is heavier than air, unlike natural gas, and thus will flow along floors and tend to settle in low spots, such as basements. There are two main dangers from this. The first is a possible explosion if the mixture of LPG and air is within the explosive limits and there is an ignition source. The second is suffocation due to LPG displacing air, causing a decrease in oxygen concentration.
Large amounts of LPG can be stored in bulk cylinders and can be buried underground.

Uses

Rural heating

Predominantly in Europe and rural parts of many countries, LPG can provide an alternative to electricity and heating oil (kerosene). LPG is most often used where there is no access to piped natural gas.

LPG can be used as a power source for combined heat and power technologies (CHP). CHP is the process of generating both electrical power and useful heat from a single fuel source. This technology has allowed LPG to be used not just as fuel for heating and cooking, but also for de-centralised generation of electricity.

LPG can be stored in a variety of ways. LPG, as with other fossil fuels, can be combined with renewable power sources to provide greater reliability while still achieving some reduction in CO₂ emissions.

Motor fuel

When LPG is used to fuel internal combustion engines, it is often referred to as autogas or auto propane. In some countries, it has been used since the 1940s as a petrol alternative for spark ignition engines. In some countries, there are additives in the liquid that extend engine life and the ratio of butane to propane is kept quite precise in fuel LPG. Two recent studies have examined LPG-fuel-oil fuel mixes and found that smoke emissions and fuel consumption are reduced but hydrocarbon emissions are increased. The studies were split on CO emissions, with one finding significant increases, and the other finding slight increases at low engine load but a considerable decrease at high engine load. Its advantage is that it is non-toxic, non-corrosive and free of tetraethyllead or any additives, and has a high octane rating (102–108 RON depending on local specifications). It burns more cleanly than petrol or fuel-oil and is especially free of the particulates present in the latter.

LPG has a lower energy density than either petrol or fuel-oil, so the equivalent fuel consumption is higher. Many governments impose less tax on LPG than on petrol or fuel-oil, which helps offset the greater consumption of LPG than of petrol or fuel-oil. However, in many European countries this tax break is often compensated by a much higher annual road tax on cars using LPG than on cars using petrol or fuel-oil. Propane is the third most widely used motor fuel in the world. 2008 estimates are that over 13 million vehicles are fueled by propane gas worldwide. Over 20 million tonnes (over 7 billion US gallons) are used annually as a vehicle fuel.

Not all automobile engines are suitable for use with LPG as a fuel. LPG provides less upper cylinder lubrication than petrol or diesel, so LPG-fueled engines are more prone to valve wear if they are not suitably modified. Many modern common rail diesel engines respond well to LPG use as a supplementary fuel. This is where LPG is used as fuel as well as diesel. Systems are now available that integrate with OEM engine management systems.

Refrigeration

LPG is instrumental in providing off-the-grid refrigeration, usually by means of a gas absorption refrigerator.

Blended of pure, dry propane (refrigerant designator R-290) and isobutane (R-600a) the blend "R-290a" has negligible ozone depletion potential and very low global warming potential and can serve as a functional replacement for R-12, R-22, R-134a and other chlorofluorocarbon or hydrofluorocarbon refrigerants in conventional stationary refrigeration and air conditioning systems.

Such substitution is widely prohibited or discouraged in motor vehicle air conditioning systems, on the grounds that using flammable hydrocarbons in systems originally designed to carry non-flammable refrigerant presents a significant risk of fire or explosion.

Vendors and advocates of hydrocarbon refrigerants argue against such bans on the grounds that there have been very few such incidents relative to the number of vehicle air conditioning systems filled with hydrocarbons. One particular test, conducted by a professor at the University of New South Wales, unintentionally tested the worst-case scenario of a sudden and complete refrigerant expulsion into the passenger compartment followed by subsequent ignition. He and several others in the car sustained minor burns to their face, ears, and hands, and several observers received lacerations from the burst glass of the front passenger window. No one was seriously injured.

Cooking

LPG is used for cooking in many countries for economic reasons, for convenience or because it is the preferred fuel source.

According to the 2011 census of India, 33.6 million (28.5%) Indian households used LPG as cooking fuel in 2011, which is supplied to their homes either in pressurised cylinders or through pipes. LPG is subsidised by the government in India. Increase in LPG prices has been a politically sensitive matter in India as it potentially affects the urban middle class voting pattern.

LPG was once a popular cooking fuel in Hong Kong; however, the continued expansion of town gas to buildings has reduced LPG usage to less than 24% of residential units.

LPG is the most common cooking fuel in Brazilian urban areas, being used in virtually all households, with the exception of the cities of Rio de Janeiro and São Paulo, which have a natural gas pipeline infrastructure. Poor families receive a government grant ("Vale Gás") used exclusively for the acquisition of LPG.

LPG is commonly used in North America for domestic cooking and outdoor grilling.

Security of supply

Because of the natural gas and the oil-refining industry, Europe is almost self-sufficient in LPG. Europe's security of supply is further safeguarded by:

• a wide range of sources, both inside and outside Europe;
• a flexible supply chain via water, rail and road with numerous routes and entry points into Europe;

According to 2010–12 estimates, proven world reserves of natural gas, from which most LPG is derived, stand at 300 trillion cubic meters (10,600 trillion cubic feet). Added to the LPG derived from cracking crude oil, this amounts to a major energy source that is virtually untapped and has massive potential. Production continues to grow at an average annual rate of 2.2%, virtually assuring that there is no risk of demand outstripping supply in the foreseeable future.

Comparison with natural gas

LPG is composed primarily of propane and butane§, while natural gas is composed of the lighter methane and ethane. LPG, vaporised and at atmospheric pressure, has a higher calorific value (94 MJ/m³ equivalent to 26.1kWh/m³) than natural gas (methane) (38 MJ/m³ equivalent to 10.6 kWh/m³), which means that LPG cannot simply be substituted for natural gas. In order to allow the use of the same burner controls and to provide for similar combustion characteristics, LPG can be mixed with air to produce a synthetic natural gas (SNG) that can be easily substituted. LPG/air mixing ratios average 60/40, though this is widely variable based on the gases making up the LPG. The method for determining the mixing ratios is by calculating the Wobbe index of the mix. Gases having the same Wobbe index are held to be interchangeable.

LPG-based SNG is used in emergency backup systems for many public, industrial and military installations, and many utilities use LPG peak shaving plants in times of high demand to make up shortages in natural gas supplied to their distributions systems. LPG-SNG installations are also used during initial gas system introductions, when the distribution infrastructure is in place before gas supplies can be connected. Developing markets in India and China (among others) use LPG-SNG systems to build up customer bases prior to expanding existing natural gas systems.

LPG-based SNG or natural gas with localized storage and piping distribution network to the house holds for catering to each cluster of 5000 domestic consumers can be planned under initial phase of city gas network system. This would eliminate the last mile LPG cylinders road transport which is a cause of traffic and safety hurdles in Indian cities. These localized natural gas networks are successfully operating in Japan with feasibility to get connected to wider networks in both villages and cities.

Environmental effects

Commercially available LPG is currently derived from fossil fuels. Burning LPG releases carbon dioxide, a greenhouse gas. The reaction also produces some carbon monoxide. LPG does, however, release less CO2 per unit of energy than does coal or oil. It emits 81% of the CO2 per kWh produced by oil, 70% of that of coal, and less than 50% of that emitted by coal-generated electricity distributed via the grid. Being a mix of propane and butane, LPG emits less carbon per joule than butane but more carbon per joule than propane.

LPG can be considered to burn more cleanly than heavier molecule hydrocarbons, in that it releases very few particulates.

Fire/explosion risk and mitigation

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In a refinery or gas plant, LPG must be stored in pressure vessels. These containers are either cylindrical and horizontal or spherical. Typically, these vessels are designed and manufactured according to some code. In the United States, this code is governed by the American Society of Mechanical Engineers (ASME).LPG containers have pressure relief valves, such that when subjected to exterior heating sources, they will vent LPGs to the atmosphere.If a tank is subjected to a fire of sufficient duration and intensity, it can undergo a boiling liquid expanding vapor explosion (BLEVE). This is typically a concern for large refineries and petrochemical plants that maintain very large containers. In general, tanks are designed that the product will vent faster than pressure can build to dangerous levels.One remedy, that is utilized in industrial settings, is to equip such containers with a measure to provide a fire-resistance rating. Large, spherical LPG containers may have up to a 15 cm steel wall thickness. They are equipped with an approved pressure relief valve. A large fire in the vicinity of the vessel will increase its temperature and pressure, following the basic gas laws. The relief valve on the top is designed to vent off excess pressure in order to prevent the rupture of the container itself. Given a fire of sufficient duration and intensity, the pressure being generated by the boiling and expanding gas can exceed the ability of the valve to vent the excess. If that occurs, an overexposed container may rupture violently, launching pieces at high velocity, while the released products can ignite as well, potentially causing catastrophic damage to anything nearby, including other containers.

                            HYDROGEN

Hydrogen is a chemical element with chemical symbol H and atomic number 1. With an atomic weight of 1.00794 u, hydrogen is the lightest element on the periodic table. Its monatomic form (H) is the most abundant chemical substance in the universe, constituting roughly 75% of all baryonic mass. Non-remnant stars are mainly composed of hydrogen in its plasma state. The most common isotope of hydrogen, termed protium (name rarely used, symbol ¹H), has a single proton and zero neutrons.
The universal emergence of atomic hydrogen first occurred during the recombination epoch. At standard temperature and pressure, hydrogen is a colorless, odorless, tasteless, non-toxic, nonmetallic, highly combustible diatomic gas with the molecular formula H₂. Since hydrogen readily forms covalent compounds with most non-metallic elements, most of the hydrogen on Earth exists in molecular forms such as in the form of water or organic compounds. Hydrogen plays a particularly important role in acid–base reactions. In ionic compounds, hydrogen can take the form of a negative charge (i.e., anion) known as a hydride, or as a positively charged (i.e., cation) species denoted by the symbol H⁺. The hydrogen cation is written as though composed of a bare proton, but in reality, hydrogen cations in ionic compounds are always more complex species than that would suggest. Hydrogen can form compounds with most elements and is present in water and most organic compounds. It plays a particularly important role in acid-base chemistry, in which many reactions involve the exchange of protons between soluble molecules. As the only neutral atom for which the Schrödinger equation can be solved analytically, study of the energetics and bonding of the hydrogen atom has played a key role in the development of quantum mechanics.
Hydrogen gas was first artificially produced in the early 16th century, via the mixing of metals with acids. In 1766–81, Henry Cavendish was the first to recognize that hydrogen gas was a discrete substance, and that it produces water when burned, a property which later gave it its name: in Greek, hydrogen means "water-former".
Industrial production is mainly from the steam reforming of natural gas, and less often from more energy-intensive hydrogen production methods like the electrolysis of water. Most hydrogen is employed near its production site, with the two largest uses being fossil fuel processing (e.g., hydrocracking) and ammonia production, mostly for the fertilizer market.
Hydrogen is a concern in metallurgy as it can embrittle many metals, complicating the design of pipelines and storage tanks.

 

 

Properties

Combustion

Hydrogen gas (dihydrogen or molecular hydrogen) is highly flammable and will burn in air at a very wide range of concentrations between 4% and 75% by volume. The enthalpy of combustion for hydrogen is −286 kJ/mol:

2 H₂(g) + O₂(g) → 2 H₂O(l) + 572 kJ (286 kJ/mol)

Hydrogen gas forms explosive mixtures with air if it is 4–74% concentrated and with chlorine if it is 5–95% concentrated. The mixtures may be ignited by spark, heat or sunlight. The hydrogen autoignition temperature, the temperature of spontaneous ignition in air, is 500 °C (932 °F). Pure hydrogen-oxygen flames emit ultraviolet light and with high oxygen mix are nearly invisible to the naked eye, as illustrated by the faint plume of the Space Shuttle Main Engine compared to the highly visible plume of a Space Shuttle Solid Rocket Booster. The detection of a burning hydrogen leak may require a flame detector; such leaks can be very dangerous. Hydrogen flames in other conditions are blue, resembling blue natural gas flames. The destruction of the Hindenburg airship was an infamous example of hydrogen combustion; the cause is debated, but the visible orange flames were the result of a rich mixture of hydrogen to oxygen combined with carbon compounds from the airship skin.
H₂ reacts with every oxidizing element. Hydrogen can react spontaneously and violently at room temperature with chlorine and fluorine to form the corresponding hydrogen halides, hydrogen chloride and hydrogen fluoride, which are also potentially dangerous acids.

Electron energy levels

Main article: Hydrogen atom

The ground state energy level of the electron in a hydrogen atom is −13.6 eV, which is equivalent to an ultraviolet photon of roughly 92 nm wavelength.
The energy levels of hydrogen can be calculated fairly accurately using the Bohr model of the atom, which conceptualizes the electron as "orbiting" the proton in analogy to the Earth's orbit of the Sun. However, the electromagnetic force attracts electrons and protons to one another, while planets and celestial objects are attracted to each other by gravity. Because of the discretization of angular momentum postulated in early quantum mechanics by Bohr, the electron in the Bohr model can only occupy certain allowed distances from the proton, and therefore only certain allowed energies.
A more accurate description of the hydrogen atom comes from a purely quantum mechanical treatment that uses the Schrödinger equation or the Feynman path integral formulation to calculate the probability density of the electron around the proton. The most complicated treatments allow for the small effects of special relativity and vacuum polarization. In the quantum mechanical treatment, the electron in a ground state hydrogen atom has no angular momentum at all—an illustration of how the "planetary orbit" conception of electron motion differs from reality.

Elemental molecular forms

There exist two different spin isomers of hydrogen diatomic molecules that differ by the relative spin of their nuclei. In the orthohydrogen form, the spins of the two protons are parallel and form a triplet state with a molecular spin quantum number of 1 (¹⁄₂+¹⁄₂); in the parahydrogen form the spins are antiparallel and form a singlet with a molecular spin quantum number of 0 (¹⁄₂–¹⁄₂). At standard temperature and pressure, hydrogen gas contains about 25% of the para form and 75% of the ortho form, also known as the "normal form". The equilibrium ratio of orthohydrogen to parahydrogen depends on temperature, but because the ortho form is an excited state and has a higher energy than the para form, it is unstable and cannot be purified. At very low temperatures, the equilibrium state is composed almost exclusively of the para form. The liquid and gas phase thermal properties of pure parahydrogen differ significantly from those of the normal form because of differences in rotational heat capacities, as discussed more fully in spin isomers of hydrogen. The ortho/para distinction also occurs in other hydrogen-containing molecules or functional groups, such as water and methylene, but is of little significance for their thermal properties.
The uncatalyzed interconversion between para and ortho H₂ increases with increasing temperature; thus rapidly condensed H₂ contains large quantities of the high-energy ortho form that converts to the para form very slowly. The ortho/para ratio in condensed H₂ is an important consideration in the preparation and storage of liquid hydrogen: the conversion from ortho to para is exothermic and produces enough heat to evaporate some of the hydrogen liquid, leading to loss of liquefied material. Catalysts for the ortho-para interconversion, such as ferric oxide, activated carbon, platinized asbestos, rare earth metals, uranium compounds, chromic oxide, or some nickel compounds, are used during hydrogen cooling.

Phases

• Compressed hydrogen
• Liquid hydrogen
• Slush hydrogen
• Solid hydrogen
• Metallic hydrogen

Compounds

Further information: Hydrogen compounds

Covalent and organic compounds

While H₂ is not very reactive under standard conditions, it does form compounds with most elements. Hydrogen can form compounds with elements that are more electronegative, such as halogens (e.g., F, Cl, Br, I), or oxygen; in these compounds hydrogen takes on a partial positive charge. When bonded to fluorine, oxygen, or nitrogen, hydrogen can participate in a form of medium-strength noncovalent bonding called hydrogen bonding, which is critical to the stability of many biological molecules. Hydrogen also forms compounds with less electronegative elements, such as the metals and metalloids, in which it takes on a partial negative charge. These compounds are often known as hydrides.
Hydrogen forms a vast array of compounds with carbon called the hydrocarbons, and an even vaster array with heteroatoms that, because of their general association with living things, are called organic compounds. The study of their properties is known as organic chemistry and their study in the context of living organisms is known as biochemistry. By some definitions, "organic" compounds are only required to contain carbon. However, most of them also contain hydrogen, and because it is the carbon-hydrogen bond which gives this class of compounds most of its particular chemical characteristics, carbon-hydrogen bonds are required in some definitions of the word "organic" in chemistry. Millions of hydrocarbons are known, and they are usually formed by complicated synthetic pathways, which seldom involve elementary hydrogen.

Hydrides

Compounds of hydrogen are often called hydrides, a term that is used fairly loosely. The term "hydride" suggests that the H atom has acquired a negative or anionic character, denoted H⁻, and is used when hydrogen forms a compound with a more electropositive element. The existence of the hydride anion, suggested by Gilbert N. Lewis in 1916 for group I and II salt-like hydrides, was demonstrated by Moers in 1920 by the electrolysis of molten lithium hydride (LiH), producing a stoichiometry quantity of hydrogen at the anode. For hydrides other than group I and II metals, the term is quite misleading, considering the low electronegativity of hydrogen. An exception in group II hydrides is BeH2, which is polymeric. In lithium aluminium hydride, the AlH−4 anion carries hydridic centers firmly attached to the Al(III).
Although hydrides can be formed with almost all main-group elements, the number and combination of possible compounds varies widely; for example, there are over 100 binary borane hydrides known, but only one binary aluminium hydride. Binary indium hydride has not yet been identified, although larger complexes exist.
In inorganic chemistry, hydrides can also serve as bridging ligands that link two metal centers in a coordination complex. This function is particularly common in group 13 elements, especially in boranes (boron hydrides) and aluminium complexes, as well as in clustered carboranes.

Protons and acids

Further information: Acid–base reaction

Oxidation of hydrogen removes its electron and gives H⁺, which contains no electrons and a nucleus which is usually composed of one proton. That is why H+
is often called a proton. This species is central to discussion of acids. Under the Bronsted-Lowry theory, acids are proton donors, while bases are proton acceptors.
A bare proton, H+
, cannot exist in solution or in ionic crystals, because of its unstoppable attraction to other atoms or molecules with electrons. Except at the high temperatures associated with plasmas, such protons cannot be removed from the electron clouds of atoms and molecules, and will remain attached to them. However, the term 'proton' is sometimes used loosely and metaphorically to refer to positively charged or cationic hydrogen attached to other species in this fashion, and as such is denoted "H+
" without any implication that any single protons exist freely as a species.
To avoid the implication of the naked "solvated proton" in solution, acidic aqueous solutions are sometimes considered to contain a less unlikely fictitious species, termed the "hydronium ion" (H3O+). However, even in this case, such solvated hydrogen cations are more realistically conceived as being organized into clusters that form species closer to H9O+4. Other oxonium ions are found when water is in acidic solution with other solvents.
Although exotic on Earth, one of the most common ions in the universe is the H+3 ion, known as protonated molecular hydrogen or the trihydrogen cation.

Isotopes

Main article: Isotopes of hydrogen

Protium, the most common isotope of hydrogen, has one proton and one electron. Unique among all stable isotopes, it has no neutrons (see diproton for a discussion of why others do not exist).

Hydrogen has three naturally occurring isotopes, denoted 1H, 2H and 3H. Other, highly unstable nuclei (4H to 7H) have been synthesized in the laboratory but not observed in nature.

• 1
  H is the most common hydrogen isotope with an abundance of more than 99.98%. Because the nucleus of this isotope consists of only a single proton, it is given the descriptive but rarely used formal name protium.
• 2
  H, the other stable hydrogen isotope, is known as deuterium and contains one proton and one neutron in its nucleus. Essentially all deuterium in the universe is thought to have been produced at the time of the Big Bang, and has endured since that time. Deuterium is not radioactive, and does not represent a significant toxicity hazard. Water enriched in molecules that include deuterium instead of normal hydrogen is called heavy water. Deuterium and its compounds are used as a non-radioactive label in chemical experiments and in solvents for 1
  H-NMR spectroscopy. Heavy water is used as a neutron moderator and coolant for nuclear reactors. Deuterium is also a potential fuel for commercial nuclear fusion.
• 3
  H is known as tritium and contains one proton and two neutrons in its nucleus. It is radioactive, decaying into helium-3 through beta decay with a half-life of 12.32 years. It is so radioactive that it can be used in luminous paint, making it useful in such things as watches. The glass prevents the small amount of radiation from getting out. Small amounts of tritium occur naturally because of the interaction of cosmic rays with atmospheric gases; tritium has also been released during nuclear weapons tests. It is used in nuclear fusion reactions, as a tracer in isotope geochemistry, and specialized in self-powered lighting devices. Tritium has also been used in chemical and biological labeling experiments as a radiolabel.

Hydrogen is the only element that has different names for its isotopes in common use today. During the early study of radioactivity, various heavy radioactive isotopes were given their own names, but such names are no longer used, except for deuterium and tritium. The symbols D and T (instead of 2H and 3H) are sometimes used for deuterium and tritium, but the corresponding symbol for protium, P, is already in use for phosphorus and thus is not available for protium. In its nomenclatural guidelines, the International Union of Pure and Applied Chemistry allows any of D, T, 2H, and 3H to be used, although 2H and 3H are preferred.

History

Discovery and use

Main article: Timeline of hydrogen technologies

In 1671, Robert Boyle discovered and described the reaction between iron filings and dilute acids, which results in the production of hydrogen gas. In 1766, Henry Cavendish was the first to recognize hydrogen gas as a discrete substance, by naming the gas from a metal-acid reaction "flammable air". He speculated that "flammable air" was in fact identical to the hypothetical substance called "phlogiston" and further finding in 1781 that the gas produces water when burned. He is usually given credit for its discovery as an element. In 1783, Antoine Lavoisier gave the element the name hydrogen (from the Greek ὑδρο- hydro meaning "water" and -γενής genes meaning "creator") when he and Laplace reproduced Cavendish's finding that water is produced when hydrogen is burned.
Lavoisier produced hydrogen for his experiments on mass conservation by reacting a flux of steam with metallic iron through an incandescent iron tube heated in a fire. Anaerobic oxidation of iron by the protons of water at high temperature can be schematically represented by the set of following reactions:

   Fe +    H₂O → FeO + H₂

2 Fe + 3 H₂O → Fe₂O₃ + 3 H₂

3 Fe + 4 H₂O → Fe₃O₄ + 4 H₂

Many metals such as zirconium undergo a similar reaction with water leading to the production of hydrogen.
Hydrogen was liquefied for the first time by James Dewar in 1898 by using regenerative cooling and his invention, the vacuum flask. He produced solid hydrogen the next year. Deuterium was discovered in December 1931 by Harold Urey, and tritium was prepared in 1934 by Ernest Rutherford, Mark Oliphant, and Paul Harteck. Heavy water, which consists of deuterium in the place of regular hydrogen, was discovered by Urey's group in 1932. François Isaac de Rivaz built the first de Rivaz engine, an internal combustion engine powered by a mixture of hydrogen and oxygen in 1806. Edward Daniel Clarke invented the hydrogen gas blowpipe in 1819. The Döbereiner's lamp and limelight were invented in 1823.
The first hydrogen-filled balloon was invented by Jacques Charles in 1783. Hydrogen provided the lift for the first reliable form of air-travel following the 1852 invention of the first hydrogen-lifted airship by Henri Giffard. German count Ferdinand von Zeppelin promoted the idea of rigid airships lifted by hydrogen that later were called Zeppelins; the first of which had its maiden flight in 1900. Regularly scheduled flights started in 1910 and by the outbreak of World War I in August 1914, they had carried 35,000 passengers without a serious incident. Hydrogen-lifted airships were used as observation platforms and bombers during the war.
The first non-stop transatlantic crossing was made by the British airship R34 in 1919. Regular passenger service resumed in the 1920s and the discovery of helium reserves in the United States promised increased safety, but the U.S. government refused to sell the gas for this purpose. Therefore, H₂ was used in the Hindenburg airship, which was destroyed in a midair fire over New Jersey on 6 May 1937. The incident was broadcast live on radio and filmed. Ignition of leaking hydrogen is widely assumed to be the cause, but later investigations pointed to the ignition of the aluminized fabric coating by static electricity. But the damage to hydrogen's reputation as a lifting gas was already done.
In the same year the first hydrogen-cooled turbogenerator went into service with gaseous hydrogen as a coolant in the rotor and the stator in 1937 at Dayton, Ohio, by the Dayton Power & Light Co, because of the thermal conductivity of hydrogen gas this is the most common type in its field today.
The nickel hydrogen battery was used for the first time in 1977 aboard the U.S. Navy's Navigation technology satellite-2 (NTS-2). For example, the ISS, Mars Odyssey and the Mars Global Surveyor are equipped with nickel-hydrogen batteries. In the dark part of its orbit, the Hubble Space Telescope is also powered by nickel-hydrogen batteries, which were finally replaced in May 2009, more than 19 years after launch, and 13 years over their design life.

Role in quantum theory

Because of its relatively simple atomic structure, consisting only of a proton and an electron, the hydrogen atom, together with the spectrum of light produced from it or absorbed by it, has been central to the development of the theory of atomic structure. Furthermore, the corresponding simplicity of the hydrogen molecule and the corresponding cation H+2 allowed fuller understanding of the nature of the chemical bond, which followed shortly after the quantum mechanical treatment of the hydrogen atom had been developed in the mid-1920s.
One of the first quantum effects to be explicitly noticed (but not understood at the time) was a Maxwell observation involving hydrogen, half a century before full quantum mechanical theory arrived. Maxwell observed that the specific heat capacity of H₂ unaccountably departs from that of a diatomic gas below room temperature and begins to increasingly resemble that of a monatomic gas at cryogenic temperatures. According to quantum theory, this behavior arises from the spacing of the (quantized) rotational energy levels, which are particularly wide-spaced in H₂ because of its low mass. These widely spaced levels inhibit equal partition of heat energy into rotational motion in hydrogen at low temperatures. Diatomic gases composed of heavier atoms do not have such widely spaced levels and do not exhibit the same effect.

Natural occurrence

Hydrogen, as atomic H, is the most abundant chemical element in the universe, making up 75% of normal matter by mass and over 90% by number of atoms (most of the mass of the universe, however, is not in the form of chemical-element type matter, but rather is postulated to occur as yet-undetected forms of mass such as dark matter and dark energy). This element is found in great abundance in stars and gas giant planets. Molecular clouds of H₂ are associated with star formation. Hydrogen plays a vital role in powering stars through the proton-proton reaction and the CNO cycle nuclear fusion.
Throughout the universe, hydrogen is mostly found in the atomic and plasma states whose properties are quite different from molecular hydrogen. As a plasma, hydrogen's electron and proton are not bound together, resulting in very high electrical conductivity and high emissivity (producing the light from the Sun and other stars). The charged particles are highly influenced by magnetic and electric fields. For example, in the solar wind they interact with the Earth's magnetosphere giving rise to Birkeland currents and the aurora. Hydrogen is found in the neutral atomic state in the interstellar medium. The large amount of neutral hydrogen found in the damped Lyman-alpha systems is thought to dominate the cosmological baryonic density of the Universe up to redshift z=4.
Under ordinary conditions on Earth, elemental hydrogen exists as the diatomic gas, H₂ (for data see table). However, hydrogen gas is very rare in the Earth's atmosphere (1 ppm by volume) because of its light weight, which enables it to escape from Earth's gravity more easily than heavier gases. However, hydrogen is the third most abundant element on the Earth's surface, mostly in the form of chemical compounds such as hydrocarbons and water. Hydrogen gas is produced by some bacteria and algae and is a natural component of flatus, as is methane, itself a hydrogen source of increasing importance.
A molecular form called protonated molecular hydrogen (H+3) is found in the interstellar medium, where it is generated by ionization of molecular hydrogen from cosmic rays. This charged ion has also been observed in the upper atmosphere of the planet Jupiter. The ion is relatively stable in the environment of outer space due to the low temperature and density. H+3 is one of the most abundant ions in the Universe, and it plays a notable role in the chemistry of the interstellar medium. Neutral triatomic hydrogen H₃ can only exist in an excited form and is unstable. By contrast, the positive hydrogen molecular ion (H+2) is a rare molecule in the universe.

Production

Main article: Hydrogen production

H2 is produced in chemistry and biology laboratories, often as a by-product of other reactions; in industry for the hydrogenation of unsaturated substrates; and in nature as a means of expelling reducing equivalents in biochemical reactions.

Metal-acid

In the laboratory, H2 is usually prepared by the reaction of dilute non-oxidizing acids on some reactive metals such as zinc with Kipp's apparatus.

Zn + 2 H+→ Zn2+ H2

Aluminium can also produce H2 upon treatment with bases:

2 Al + 6 H2O + 2 OH−→ 2 Al(OH)−4 + 3 H2

The electrolysis of water is a simple method of producing hydrogen. A low voltage current is run through the water, and gaseous oxygen forms at the anode while gaseous hydrogen forms at the cathode. Typically the cathode is made from platinum or another inert metal when producing hydrogen for storage. If, however, the gas is to be burnt on site, oxygen is desirable to assist the combustion, and so both electrodes would be made from inert metals. (Iron, for instance, would oxidize, and thus decrease the amount of oxygen given off.) The theoretical maximum efficiency (electricity used vs. energetic value of hydrogen produced) is in the range 80–94%.

2 H2O(l) → 2 H2(g) + O2(g)

In 2007, it was discovered that an alloy of aluminium and gallium in pellet form added to water could be used to generate hydrogen. The process also creates alumina, but the expensive gallium, which prevents the formation of an oxide skin on the pellets, can be re-used. This has important potential implications for a hydrogen economy, as hydrogen can be produced on-site and does not need to be transported.

Steam reforming

Hydrogen can be prepared in several different ways, but economically the most important processes involve removal of hydrogen from hydrocarbons. Commercial bulk hydrogen is usually produced by the steam reforming of natural gas. At high temperatures (1000–1400 K, 700–1100 °C or 1300–2000 °F), steam (water vapor) reacts with methane to yield carbon monoxide and H2.

CH4 + H2O → CO + 3 H2

This reaction is favored at low pressures but is nonetheless conducted at high pressures (2.0  MPa, 20 atm or 600 inHg). This is because high-pressure H2 is the most marketable product and Pressure Swing Adsorption (PSA) purification systems work better at higher pressures. The product mixture is known as "synthesis gas" because it is often used directly for the production of methanol and related compounds. Hydrocarbons other than methane can be used to produce synthesis gas with varying product ratios. One of the many complications to this highly optimized technology is the formation of coke or carbon:

CH4 → C + 2 H2

Consequently, steam reforming typically employs an excess of H2O. Additional hydrogen can be recovered from the steam by use of carbon monoxide through the water gas shift reaction, especially with an iron oxide catalyst. This reaction is also a common industrial source of carbon dioxide:

CO + H2O → CO2 + H2

Other important methods for H2 production include partial oxidation of hydrocarbons:

2 CH4 + O2 → 2 CO + 4 H2

and the coal reaction, which can serve as a prelude to the shift reaction above:

C + H2O → CO + H2

Hydrogen is sometimes produced and consumed in the same industrial process, without being separated. In the Haber process for the production of ammonia, hydrogen is generated from natural gas. Electrolysis of brine to yield chlorine also produces hydrogen as a co-product.

Thermochemical

There are more than 200 thermochemical cycles which can be used for water splitting, around a dozen of these cycles such as the iron oxide cycle, cerium(IV) oxide–cerium(III) oxide cycle, zinc zinc-oxide cycle, sulfur-iodine cycle, copper-chlorine cycle and hybrid sulfur cycle are under research and in testing phase to produce hydrogen and oxygen from water and heat without using electricity. A number of laboratories (including in France, Germany, Greece, Japan, and the USA) are developing thermochemical methods to produce hydrogen from solar energy and water.

Anaerobic corrosion

Under anaerobic conditions, iron and steel alloys are slowly oxidized by the protons of water concomitantly reduced in molecular hydrogen (H2). The anaerobic corrosion of iron leads first to the formation of ferrous hydroxide (green rust) and can be described by the following reaction:

Fe + 2 H2O → Fe(OH)2 + H2

In its turn, under anaerobic conditions, the ferrous hydroxide (Fe(OH)2 ) can be oxidized by the protons of water to form magnetite and molecular hydrogen. This process is described by the Schikorr reaction:

3 Fe(OH)2 → Fe3O4 + 2 H2O + H2

ferrous hydroxide → magnetite + water + hydrogen

The well crystallized magnetite (Fe3O4) is thermodynamically more stable than the ferrous hydroxide (Fe(OH)2 ).
This process occurs during the anaerobic corrosion of iron and steel in oxygen-free groundwater and in reducing soils below the water table.

Geological occurrence: the serpentinization reaction

In the absence of atmospheric oxygen (O2), in deep geological conditions prevailing far away from Earth atmosphere, hydrogen (H2) is produced during the process of serpentinization by the anaerobic oxidation by the water protons (H⁺) of the ferrous (Fe²⁺) silicate present in the crystal lattice of the fayalite (Fe2SiO4, the olivine iron-endmember). The corresponding reaction leading to the formation of magnetite (Fe3O4), quartz (SiO2) and hydrogen (H2) is the following:

3Fe2SiO4 + 2 H2O → 2 Fe3O4 + 3 SiO2 + 3 H2

fayalite + water → magnetite + quartz + hydrogen

This reaction closely resembles the Schikorr reaction observed in the anaerobic oxidation of the ferrous hydroxide in contact with water.

Formation in transformers

From all the fault gases formed in power transformers, hydrogen is the most common and is generated under most fault conditions; thus, formation of hydrogen is an early indication of serious problems in the transformer's life cycle.

Xylose

In 2014 a low-temperature 50 °C (122 °F), atmospheric-pressure enzyme-driven process to convert xylose into hydrogen with nearly 100% of the theoretical yield was announced. The process employs 13 enzymes, including a novel polyphosphate xylulokinase (XK).

Applications

Consumption in processes

Large quantities of H2 are needed in the petroleum and chemical industries. The largest application of H2 is for the processing ("upgrading") of fossil fuels, and in the production of ammonia. The key consumers of H2 in the petrochemical plant include hydrodealkylation, hydrodesulfurization, and hydrocracking. H2 has several other important uses. H2 is used as a hydrogenating agent, particularly in increasing the level of saturation of unsaturated fats and oils (found in items such as margarine), and in the production of methanol. It is similarly the source of hydrogen in the manufacture of hydrochloric acid. H2 is also used as a reducing agent of metallic ores.
Hydrogen is highly soluble in many rare earth and transition metals and is soluble in both nanocrystalline and amorphous metals. Hydrogen solubility in metals is influenced by local distortions or impurities in the crystal lattice. These properties may be useful when hydrogen is purified by passage through hot palladium disks, but the gas's high solubility is a metallurgical problem, contributing to the embrittlement of many metals, complicating the design of pipelines and storage tanks.
Apart from its use as a reactant, H2 has wide applications in physics and engineering. It is used as a shielding gas in welding methods such as atomic hydrogen welding. H₂ is used as the rotor coolant in electrical generators at power stations, because it has the highest thermal conductivity of any gas. Liquid H₂ is used in cryogenic research, including superconductivity studies. Because H2 is lighter than air, having a little more than ¹⁄₁₄ of the density of air, it was once widely used as a lifting gas in balloons and airships.
In more recent applications, hydrogen is used pure or mixed with nitrogen (sometimes called forming gas) as a tracer gas for minute leak detection. Applications can be found in the automotive, chemical, power generation, aerospace, and telecommunications industries. Hydrogen is an authorized food additive (E 949) that allows food package leak testing among other anti-oxidizing properties.
Hydrogen's rarer isotopes also each have specific applications. Deuterium (hydrogen-2) is used in nuclear fission applications as a moderator to slow neutrons, and in nuclear fusion reactions. Deuterium compounds have applications in chemistry and biology in studies of reaction isotope effects. Tritium (hydrogen-3), produced in nuclear reactors, is used in the production of hydrogen bombs, as an isotopic label in the biosciences, and as a radiation source in luminous paints.
The triple point temperature of equilibrium hydrogen is a defining fixed point on the ITS-90 temperature scale at 13.8033 kelvins.

Coolant

Main article: Hydrogen-cooled turbo generator

Hydrogen is commonly used in power stations as a coolant in generators due to a number of favorable properties that are a direct result of its light diatomic molecules. These include low density, low viscosity, and the highest specific heat and thermal conductivity of all gases.

Energy carrier

Hydrogen is not an energy resource, except in the hypothetical context of commercial nuclear fusion power plants using deuterium or tritium, a technology presently far from development. The Sun's energy comes from nuclear fusion of hydrogen, but this process is difficult to achieve controllably on Earth. Elemental hydrogen from solar, biological, or electrical sources require more energy to make it than is obtained by burning it, so in these cases hydrogen functions as an energy carrier, like a battery. Hydrogen may be obtained from fossil sources (such as methane), but these sources are unsustainable.
The energy density per unit volume of both liquid hydrogen and compressed hydrogen gas at any practicable pressure is significantly less than that of traditional fuel sources, although the energy density per unit fuel mass is higher. Nevertheless, elemental hydrogen has been widely discussed in the context of energy, as a possible future carrier of energy on an economy-wide scale. For example, CO2 sequestration followed by carbon capture and storage could be conducted at the point of H2 production from fossil fuels. Hydrogen used in transportation would burn relatively cleanly, with some NO_x emissions, but without carbon emissions. However, the infrastructure costs associated with full conversion to a hydrogen economy would be substantial.

Semiconductor industry

Hydrogen is employed to saturate broken ("dangling") bonds of amorphous silicon and amorphous carbon that helps stabilizing material properties. It is also a potential electron donor in various oxide materials, including ZnO, SnO₂, CdO, MgO, ZrO₂, HfO₂, La₂O₃, Y₂O₃, TiO₂, SrTiO₃, LaAlO₃, SiO₂, Al₂O₃, ZrSiO₄, HfSiO₄, and SrZrO₃.

Biological reactions

Further information: Biohydrogen and Biological hydrogen production (Algae)

H₂ is a product of some types of anaerobic metabolism and is produced by several microorganisms, usually via reactions catalyzed by iron- or nickel-containing enzymes called hydrogenases. These enzymes catalyze the reversible redox reaction between H₂ and its component two protons and two electrons. Creation of hydrogen gas occurs in the transfer of reducing equivalents produced during pyruvate fermentation to water.
Water splitting, in which water is decomposed into its component protons, electrons, and oxygen, occurs in the light reactions in all photosynthetic organisms. Some such organisms, including the alga Chlamydomonas reinhardtii and cyanobacteria, have evolved a second step in the dark reactions in which protons and electrons are reduced to form H₂ gas by specialized hydrogenases in the chloroplast. Efforts have been undertaken to genetically modify cyanobacterial hydrogenases to efficiently synthesize H₂ gas even in the presence of oxygen. Efforts have also been undertaken with genetically modified alga in a bioreactor.

Safety and precaution

Hydrogen poses a number of hazards to human safety, from potential detonations and fires when mixed with air to being an asphyxiant in its pure, oxygen-free form. In addition, liquid hydrogen is a cryogen and presents dangers (such as frostbite) associated with very cold liquids. Hydrogen dissolves in many metals, and, in addition to leaking out, may have adverse effects on them, such as hydrogen embrittlement, leading to cracks and explosions. Hydrogen gas leaking into external air may spontaneously ignite. Moreover, hydrogen fire, while being extremely hot, is almost invisible, and thus can lead to accidental burns.

Even interpreting the hydrogen data (including safety data) is confounded by a number of phenomena. Many physical and chemical properties of hydrogen depend on the parahydrogen/orthohydrogen ratio (it often takes days or weeks at a given temperature to reach the equilibrium ratio, for which the data is usually given). Hydrogen detonation parameters, such as critical detonation pressure and temperature, strongly depend on the container geometry.