What is Ethanol
According to Wikipedia, Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a powerful psychoactive drug and one of the oldest recreational drugs. It is best known as the type of alcohol found in alcoholic beverages and thermometers. In common usage, it is often referred to simply as alcohol or spirits.
Ethanol is a straight-chain alcohol, and its molecular formula is C2H5OH. Its empirical formula is C2H6O. 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 often abbreviated as EtOH, using the common organic chemistry notation of representing the ethyl group (C2H5) with Et.
The fermentation of sugar into ethanol is one of the earliest organic reactions employed by humanity. The intoxicating effects of ethanol consumption have been known since ancient times. In modern times, ethanol intended for industrial use is also produced from by-products of petroleum refining.
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 an essential 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.
For more details on this topic, see Distilled beverage.
Ethanol being used as fuel for a burner
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 imply 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, Johann Tobias Lowitz obtained pure ethanol by filtering distilled ethanol through activated charcoal. Antoine Lavoisier described ethanol as a compound of carbon, hydrogen, and oxygen, and in 1808 Nicolas-Théodore de Saussure determined ethanol’s chemical formula. Fifty years later, Archibald Scott Couper published ethanol’s structural formula. It is one of the first structural formulas determined.
Ethanol was first prepared synthetically in 1826 through the independent efforts of Henry Hennel in Great Britain and S.G. Sérullas in France. In 1828, Michael Faraday prepared ethanol by acid-catalyzed hydration of ethylene, 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. From 1908 onward, Ford Model T automobiles could be adapted to run on ethanol. With the advent of Prohibition in 1920, ethanol fuel sellers were accused of being allied with moonshiners, and ethanol fuel fell into disuse until late in the 20th century.
 Physical properties
Ethanol burning with its spectrum depicted
Ethanol is a volatile, colorless liquid that has a strong characteristic 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.
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 that 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. At 298 K, up to 777 J/mol are set free.
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.
Thermophysical properties of mixtures of ethanol with water and dodecane Excess Volume Mixture of Ethanol and Water.png Mixing Enthalpy Mixture of Ethanol and Water.png Vapor-Liquid Equilibrium Mixture of Ethanol and Water.png
Excess volume of the mixture of ethanol and water (volume contraction) Heat of mixing of the mixture of ethanol and water Vapor-liquid equilibrium of the mixture of ethanol and water (including azeotrope)
Phase diagram ethanol water s l en.svg Liquid-Liquid Equilibrium (Miscibility Gap) Mixture of Ethanol and Dodecane.png
Solid-liquid equilibrium of the mixture of ethanol and water (including eutecticum) Miscibility gap in the mixture of dodecane and ethanol
Hydrogen bonding in solid ethanol at ?186 °C
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.
Mixtures of ethanol and water that contain more than about 50% ethanol are flammable and easily ignited. Alcoholic proof is a widely used measure of how much ethanol (i.e., alcohol) such a mixture contains. In the 18th century, proof was determined by adding a liquor (such as rum) to gunpowder. If the gunpowder still burned, that was considered to be “100 degrees proof” that it was “good” liquor — hence it was called “100 degrees proof”.
Ethanol-water solutions that contain less than 50% ethanol may also be flammable if the solution is first heated. Some cooking methods call for wine to be added to a hot pan, causing it to flash boil into a vapor, which is then ignited to burn off excess alcohol.
Ethanol is slightly more refractive than water, having a refractive index of 1.36242 (at ?=589.3 nm and 18.35 °C).
94% denatured ethanol sold in a bottle for household use
Ethanol is produced both as a petrochemical, through the hydration of ethylene, and biologically, 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 often made from petrochemical feed stocks, primarily by the acid-catalyzed hydration of ethylene, represented by the chemical equation
C2H4(g) + H2O(g) ? CH3CH2OH(l).
The catalyst is most commonly phosphoric acid, adsorbed onto a porous support such as silica gel or 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. 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 hydrolysed to yield ethanol and regenerate the sulfuric acid:
C2H4 + H2SO4 ? CH3CH2SO4H
CH3CH2SO4H + H2O ? CH3CH2OH + H2SO4
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 they produce ethanol and carbon dioxide. The chemical equation below summarizes the conversion:
C6H12O6 ? 2 CH3CH2OH + 2 CO2.
The process of culturing yeast under conditions to produce alcohol is called fermentation. This process is carried out at around 35–40 °C. Ethanol’s toxicity to yeast limits the ethanol concentration obtainable by brewing. The most ethanol-tolerant strains of yeast can survive up to approximately 15% ethanol by volume.
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.
 Cellulosic ethanol
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 also contain other polysaccharides, including hemicellulose. When undergoing hydrolysis, hemicellulose decomposes into 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.
On January 14, 2008, General Motors announced a partnership with Coskata, Inc. The goal is to produce cellulosic ethanol cheaply, with an eventual goal of US$1 per U.S. gallon ($0.30/L) for the fuel. The partnership plans to begin producing the fuel in large quantity by the end of 2008. In June 2009, this goal is still ahead of the firm. By 2011 a full-scale plant will come on line, capable of producing 50 to 100 million gallons of ethanol a year (200–400 ML/a).
 Prospective technologies
Ethanol plant in Turner County, South Dakota
The anaerobic bacterium Clostridium ljungdahlii, discovered in commercial chicken wastes, can produce ethanol from single-carbon sources including synthesis gas, a mixture of carbon monoxide and hydrogen that can be generated from the partial combustion of either fossil fuels or biomass. Use of these bacteria to produce ethanol from synthesis gas has progressed to the pilot plant stage at the BRI Energy facility in Fayetteville, Arkansas.. The BRI technology has been purchased by INEOS.
Another prospective technology is the closed-loop ethanol plant. Ethanol produced from corn has a number of critics who suggest that it is primarily just recycled fossil fuels because of the energy required to grow the grain and convert it into ethanol. There is also the issue of competition with use of corn for food production. However, the closed-loop ethanol plant attempts to address this criticism. In a closed-loop plant, renewable energy for distillation comes from fermented manure, produced from cattle that have been fed the DDSG by-products from grain ethanol production. The concentrated compost nutrients from manure are then used to fertilize the soil and grow the next crop of grain to start the cycle again. Such a process is expected to lower the fossil fuel consumption used during conversion to ethanol by 75%.
Though in an early stage of research, there is some development of alternative production methods that use feed stocks such as municipal waste or recycled products, rice hulls, sugarcane bagasse, small diameter trees, wood chips, and switchgrass.
Infrared reflection spectra of liquid ethanol, showing the -OH band centered at ~3300 cm?1 and C-H bands at ~2950 cm?1.
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.
Main article: Ethanol purification
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, and cannot be further purified by distillation.
Common methods for obtaining absolute ethanol include desiccation using adsorbents such as starch, corn grits, or zeolites, which adsorb water preferentially, as well as azeotropic distillation and extractive distillation. Most ethanol fuel refineries use an adsorbent or zeolite to desiccate the ethanol stream.
In another method to obtain absolute alcohol, a small quantity of benzene is added to rectified spirit and the mixture is then distilled. Absolute alcohol is obtained in the third fraction, which distills over at 78.3 °C (351.4 K). Because a small amount of the benzene used remains in the solution, absolute alcohol produced by this method is not suitable for consumption, as benzene is carcinogenic.
There is also an absolute alcohol production process by desiccation using glycerol. Alcohol produced by this method is known as spectroscopic alcohol—so called because the absence of benzene makes it suitable as a solvent in spectroscopy.
 Grades of ethanol
 Denatured alcohol
Main article: Denatured alcohol
Pure ethanol and alcoholic beverages are heavily taxed, 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 ethanol
Absolute or anhydrous alcohol refers to ethanol with a low water content. There are various grades with maximum water contents ranging from 1% to ppm levels. Absolute alcohol is not intended for human consumption. It may contain trace amounts of toxic benzene if azeotropic distillation is used to remove water. 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 USA, equivalent to 175 degrees proof in the UK system.
 Rectified spirits
Rectified spirit, an azeotropic composition containing 4% water, is used instead of anhydrous ethanol for various purposes. Wine spirits are about 188 proof. The impurities are different from those in 190 proof laboratory ethanol.
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 carboxylic acid. 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 a widely used diuretic.
Strong acid desiccants cause the dehydration of ethanol to form diethyl ether and other byproducts. If the Temperature of the ethanol being dehydrated exceeds around 160 °C, ethylene will be the main product. Millions of kilograms of diethyl ether are produced annually using sulfuric acid catalyst:
2 CH3CH2OH ? CH3CH2OCH2CH3 + H2O (on 120 °C)
Complete combustion of ethanol forms carbon dioxide and water:
C2H5OH + 3 O2 ? 2 CO2 + 3 H2O(l);(?Hc = ?1371 kJ/mol) 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:
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.
The largest single use of ethanol is as a motor fuel and fuel additive. Brazil has the largest national fuel ethanol industry. Gasoline sold in Brazil contains at least 25% anhydrous ethanol, but blending requirements will be reduced to 20% ethanol for a 90-day period beginning February 1, 2010 by government mandate due to low supplies of the biofuel. The U.S. has used ethanol and gasoline blends up to E85 or 15% gasoline and 85% ethanol.
USP grade ethanol for laboratory use.
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 production is praised for the high carbon sequestration capabilities of the sugar cane plantations, thus making it a real option to combat climate change.
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).
Ethanol pump station in São Paulo, Brazil where the fuel is available commercially.
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 as a surprisingly efficient fuel to produce electricity.
A Ford Taurus “fueled by clean burning ethanol” owned by New York City.
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 GL) of ethanol per year. An additional 72 construction projects underway (in the U.S.) can add 6.4 billion gallons of new capacity in the next 18 months. Over time, it is believed that a material portion of the ?150 billion gallon per year market for gasoline will begin to be replaced with fuel ethanol.
United States Postal Service vehicle running on E85, a “flex-fuel” blend in Saint Paul, Minnesota.
One problem with ethanol is that because it is easily miscible with water, it cannot be efficiently shipped through modern pipelines, like liquid hydrocarbons, over long distances. Mechanics also have seen increased cases of damage to small engines, particularly the carbureator, attributable to ethanol’s increased water retention in fuel over time.[