Ethanol

Ethanol is used in medical wipes and most commonly in antibacterial hand sanitizer gels as an antiseptic for its bactericidal and anti-fungal effects.[19] Ethanol kills microorganisms by dissolving their membrane lipid bilayer and denaturing their proteins, and is effective against most bacteria, fungi and viruses. However, it is ineffective against bacterial spores, but that can be alleviated by using hydrogen peroxide.[20] A solution of 70% ethanol is more effective than pure ethanol because ethanol relies on water molecules for optimal antimicrobial activity. Absolute ethanol may inactivate microbes without destroying them because the alcohol is unable to fully permeate the microbe's membrane.[21][22] Ethanol can also be used as a disinfectant and antiseptic because it causes cell dehydration by disrupting the osmotic balance across the cell membrane, so water leaves the cell leading to cell death.[23]

Ethanol may be administered as an antidote to ethylene glycol poisoning[24] and methanol poisoning.[25] Ethanol serves this process by acting as a competitive inhibitor against methanol and ethylene glycol for alcohol dehydrogenase.[26] Though it has more side effects, ethanol is less expensive and more readily available than fomepizole, which is also used as an antidote for methanol and ethylene glycol poisoning.[27]

Ethanol, often in high concentrations, is used to dissolve many water-insoluble medications and related compounds. Liquid preparations of pain medications, cough and cold medicines, and mouth washes, for example, may contain up to 25% ethanol[28] and may need to be avoided in individuals with adverse reactions to ethanol such as alcohol-induced respiratory reactions.[29] Ethanol is present mainly as an antimicrobial preservative in over 700 liquid preparations of medicine including acetaminophen, iron supplements, ranitidine, furosemide, mannitol, phenobarbital, trimethoprim/sulfamethoxazole and over-the-counter cough medicine.[30]

In mammals, ethanol is primarily metabolized in the liver and stomach by alcohol dehydrogenase (ADH) enzymes.[31] These enzymes catalyze the oxidation of ethanol into acetaldehyde (ethanal):[32]

CH₃CH₂OH + NAD⁺ → CH₃CHO + NADH + H⁺

When present in significant concentrations, this metabolism of ethanol is additionally aided by the cytochrome P450 enzyme CYP2E1 in humans, while trace amounts are also metabolized by catalase.[33]

The resulting intermediate, acetaldehyde, is a known carcinogen, and poses significantly greater toxicity in humans than ethanol itself. Many of the symptoms typically associated with alcohol intoxication — as well as many of the health hazards typically associated with the long-term consumption of ethanol — can be attributed to acetaldehyde toxicity in humans.[34]

The subsequent oxidation of acetaldehyde into acetate is performed by aldehyde dehydrogenase (ALDH) enzymes. A mutation in the ALDH2 gene that encodes for an inactive or dysfunctional form of this enzyme affects roughly 50% of east Asian populations, contributing to the characteristic alcohol flush reaction that can cause temporary reddening of the skin as well as a number of related, and often unpleasant, symptoms of acetaldehyde toxicity.[35] This mutation is typically accompanied by another mutation in the alcohol dehydrogenase enzyme ADH1B in roughly 80% of east Asians, which improves the catalytic efficiency of converting ethanol into acetaldehyde.[35]

As a central nervous system depressant, ethanol is one of the most commonly consumed psychoactive drugs.[36]

Despite alcohol's psychoactive and carcinogenic properties, it is readily available and legal for sale in most countries. However, there are laws regulating the sale, exportation/importation, taxation, manufacturing, consumption, and possession of alcoholic beverages. The most common regulation is prohibition for minors.

The largest single use of ethanol is as an engine fuel and fuel additive. Brazil in particular relies heavily upon the use of ethanol as an engine fuel, due in part to its role as one of the globe's leading producers of ethanol.[40][41] 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 gasoline fueled cars sold in the country. Brazilian ethanol is produced from sugar cane, which has relatively high yields (830% more fuel than the fossil fuels used to produce it) compared to some other energy crops.[42] The US and many other countries primarily use E10 (10% ethanol, sometimes known as gasohol) and E85 (85% ethanol) ethanol/gasoline mixtures.

USP grade ethanol for laboratory use.

Australian law limits the use of pure ethanol from sugarcane waste to 10% in automobiles. Older cars (and vintage cars designed to use a slower burning fuel) should have the engine valves upgraded or replaced.[43]

According to an industry advocacy group, ethanol as a fuel reduces harmful tailpipe emissions of carbon monoxide, particulate matter, oxides of nitrogen, and other ozone-forming pollutants.[44] Argonne National Laboratory analyzed greenhouse gas emissions of many different engine and fuel combinations, and found that biodiesel/petrodiesel blend (B20) showed a reduction of 8%, conventional E85 ethanol blend a reduction of 17% and cellulosic ethanol 64%, compared with pure gasoline.[45] Ethanol has a much greater research octane number (RON) than gasoline, meaning it is less prone to pre-ignition, allowing for better ignition advance which means more torque, and efficiency in addition to the lower carbon emissions.[46]

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.[47] This leads to a significantly larger photochemical reactivity and more ground level ozone.[48] This data has been assembled into The Clean Fuels Report comparison of fuel emissions[49] and show that ethanol exhaust generates 2.14 times as much ozone as gasoline exhaust.[50] When this is added into the custom Localized Pollution Index (LPI) of The Clean Fuels Report, the local pollution of ethanol (pollution that contributes to smog) is rated 1.7, where gasoline is 1.0 and higher numbers signify greater pollution.[51] 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).[52]

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.[53] More than 20% of Brazilian cars are able to use 100% ethanol as fuel, which includes ethanol-only engines and flex-fuel engines.[54] 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 fleet 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.

In the United States, the ethanol fuel industry is based largely on corn (also known as maize). According to the Renewable Fuels Association, as of 30 October 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 US) 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.[55]

Sweet sorghum is another potential source of ethanol, and is suitable for growing in dryland conditions. The International Crops Research Institute for the Semi-Arid Tropics (ICRISAT) is investigating the possibility of growing sorghum as a source of fuel, food, and animal feed in arid parts of Asia and Africa.[56] Sweet sorghum has one-third the water requirement of sugarcane over the same time period. It also requires about 22% less water than corn. The world's first sweet sorghum ethanol distillery began commercial production in 2007 in Andhra Pradesh, India.[57]

Ethanol's high miscibility with water makes it unsuitable for shipping through modern pipelines like liquid hydrocarbons.[58] Mechanics have seen increased cases of damage to small engines (in particular, the carburetor) and attribute the damage to the increased water retention by ethanol in fuel.[59]

Ethanol pump station in São Paulo, Brazil

A Ford Taurus fueled by ethanol in New York City

USPS truck running on E85 in Minnesota

Ethanol was commonly used as fuel in early bipropellant rocket (liquid-propelled) vehicles, in conjunction with an oxidizer such as liquid oxygen. The German A-4 ballistic rocket of World War II, better known by its propaganda name V-2,[60] which is credited as having begun the space age, used ethanol as the main constituent of B-Stoff. Under such nomenclature, the ethanol was mixed with 25% water to reduce the combustion chamber temperature.[61][62] The V-2's design team helped develop US rockets following World War II, including the ethanol-fueled Redstone rocket which launched the first US satellite.[63] Alcohols fell into general disuse as more energy-dense rocket fuels were developed,[62] although ethanol is currently used in lightweight rocket-powered racing aircraft.[64]

Commercial fuel cells operate on reformed natural gas, hydrogen or methanol. Ethanol is an attractive alternative due to its wide availability, low cost, high purity and low toxicity. There is a wide range of fuel cell concepts that have entered trials including direct-ethanol fuel cells, auto-thermal reforming systems and thermally integrated systems. The majority of work is being conducted at a research level although there are a number of organizations at the beginning of the commercialization of ethanol fuel cells.[65]

Ethanol fireplaces can be used for home heating or for decoration. Ethanol can also be used as stove fuel for cooking.[66][67]

Ethanol is an important industrial ingredient. It has widespread use as a precursor for other organic compounds such as ethyl halides, ethyl esters, diethyl ether, acetic acid, and ethyl amines.

Ethanol is considered a universal solvent, as its molecular structure allows for the dissolving of both polar, hydrophilic and nonpolar, hydrophobic compounds. As ethanol also has a low boiling point, it is easy to remove from a solution that has been used to dissolve other compounds, making it a popular extracting agent for botanical oils. Cannabis oil extraction methods often use ethanol as an extraction solvent,[68] and also as a post-processing solvent to remove oils, waxes, and chlorophyll from solution in a process known as winterization.

Ethanol is found in paints, tinctures, markers, and personal care products such as mouthwashes, perfumes and deodorants. However, polysaccharides precipitate from aqueous solution in the presence of alcohol, and ethanol precipitation is used for this reason in the purification of DNA and RNA.

Because of its low freezing point -173.20 °F (−114.14 °C) and low toxicity, ethanol is sometimes used in laboratories (with dry ice or other coolants) as a cooling bath to keep vessels at temperatures below the freezing point of water. For the same reason, it is also used as the active fluid in alcohol thermometers.

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.

Ethanol burning with its spectrum depicted

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's adiabatic flame temperature for combustion in air is 2082 Celsius or 3779 Fahrenheit.[69]

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).[70] The triple point for ethanol is 150 K at a pressure of 4.3 × 10⁻⁴ Pa.[71]

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. Its main use as a solvent is in making tincture of iodine, cough syrups etc.[70][72] It is also miscible with light aliphatic hydrocarbons, such as pentane and hexane, and with aliphatic chlorides such as trichloroethane and tetrachloroethylene.[72]

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.[73] 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[74]). 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.[70][75] Mixing ethanol and water is exothermic, with up to 777 J/mol[76] being released at 298 K.

Mixtures of ethanol and water form an azeotrope at about 89 mole-% ethanol and 11 mole-% water[77] or a mixture of 95.6 percent ethanol by mass (or about 97% alcohol by volume) at normal pressure, which boils at 351K (78 °C). This azeotropic composition is strongly temperature- and pressure-dependent and vanishes at temperatures below 303 K.[78]

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.[72] Sodium and potassium chlorides are slightly soluble in ethanol.[72] Because the ethanol molecule also has a nonpolar end, it will also dissolve nonpolar substances, including most essential oils[79] 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.

An ethanol–water solution will catch fire if heated above a temperature called its flash point and an ignition source is then applied to it.[80] For 20% alcohol by mass (about 25% by volume), this will occur at about 25 °C (77 °F). The flash point of pure ethanol is 13 °C (55 °F),[81] but may be influenced very slightly by atmospheric composition such as pressure and humidity. Ethanol mixtures can ignite below average room temperature. Ethanol is considered a flammable liquid (Class 3 Hazardous Material) in concentrations above 2.35% by mass (3.0% by volume; 6 proof).[82][83][84]

Flash points of ethanol–water mixtures[85][83][86]

Ethanol mass fraction, %	Temperature
	°C	°F
1	84.5	184.1[83]
2	64	147[83]
2.35	60	140[83][82]
3	51.5	124.7[83]
5	43	109[85]
6	39.5	103.1[83]
10	31	88[85]
20	25	77[83]
30	24	75[85]
40	21.9	71.4[85]
50	20	68[85][83]
60	17.9	64.2[85]
70	16	61[85]
80	15.8	60.4[83]
90	14	57[85]
100	12.5	54.5[85][83][81]

Dishes using burning alcohol for culinary effects are called flambé.

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:

C
₂H
₄ + H
₂O → CH
₃CH
₂OH

The catalyst is most commonly phosphoric acid,[96][97] 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.[98] The reaction is carried out in the presence of high pressure steam at 300 °C (572 °F) where a 5:3 ethylene to steam ratio is maintained.[99][100] This process was used on an industrial scale by Union Carbide Corporation and others in the US, but now only LyondellBasell uses it commercially.

In an older process, first practiced on the industrial scale in 1930 by Union Carbide,[101] 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:[102]

C
₂H
₄ + H
₂SO
₄ → CH
₃CH
₂SO
₄H

CH
₃CH
₂SO
₄H + H
₂O → CH
₃CH
₂OH + H
₂SO
₄

Ethanol has been produced in the laboratory by converting carbon dioxide via biological and electrochemical reactions.[103][104]

CO₂ + H
₂O → CH
₃CH
₂OH + side products

Ethanol in alcoholic beverages and fuel is produced by fermentation. Certain species of yeast (e.g., Saccharomyces cerevisiae) metabolize sugar, producing ethanol and carbon dioxide. The chemical equations below summarize the conversion:

C
₆H
₁₂O
₆ → 2 CH
₃CH
₂OH + 2 CO₂

C
₁₂H
₂₂O
₁₁ + H
₂O → 4 CH
₃CH
₂OH + 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 obtained by fortification or distillation. The most ethanol-tolerant yeast strains can survive up to approximately 18% ethanol by volume.

To produce ethanol from starchy materials such as cereals, 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.

Sugars for ethanol fermentation can be obtained from cellulose. 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 agricultural residues such as sugar cane bagasse and energy crops such as switchgrass may also be fermentable sugar sources.[105]

Infrared reflection spectra of liquid ethanol, showing the −OH band centered near 3300 cm⁻¹ and C−H bands near 2950 cm⁻¹

Near-infrared spectrum of liquid ethanol

Breweries and biofuel plants employ two methods for measuring ethanol concentration. Infrared ethanol sensors measure the vibrational frequency of dissolved ethanol using the C−H band at 2900 cm⁻¹. This method uses a relatively inexpensive solid-state sensor that compares the C−H 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.

Ethylene hydration or brewing produces an ethanol–water mixture. For most industrial and fuel uses, the ethanol must be purified. Fractional distillation at atmospheric pressure can concentrate ethanol to 95.6% by weight (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.[97]

Apart from distillation, ethanol may be dried by addition of a desiccant, such as molecular sieves, cellulose, or cornmeal. The desiccants can be dried and reused.[97] Molecular sieves can be used to selectively absorb the water from the 95.6% ethanol solution.[106] Molecular sieves of pore-size 3 Ångstrom, a type of zeolite, effectively sequester water molecules while excluding ethanol molecules. Heating the wet sieves drives out the water, allowing regeneration of their dessicant capability.[107]

Membranes can also be used to separate ethanol and water. Membrane-based separations are not subject to the limitations of the water-ethanol azeotrope because the separations are 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 the 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.

A variety of other techniques have been discussed, including the following:[97]

• Salting using potassium carbonate to exploit its insolubility will cause a phase separation with ethanol and water. This offers a very small potassium carbonate impurity to the alcohol that can be removed by distillation. This method is very useful in purification of ethanol by distillation, as ethanol forms an azeotrope with water.
• Direct electrochemical reduction of carbon dioxide to ethanol under ambient conditions using copper nanoparticles on a carbon nanospike film as the catalyst;[108]
• Extraction of ethanol from grain mash by supercritical carbon dioxide;
• Pervaporation;
• Fractional freezing is also used to concentrate fermented alcoholic solutions, such as traditionally made Applejack (beverage);
• Pressure swing adsorption.[109]

Pure ethanol and alcoholic beverages are heavily taxed as psychoactive drugs, but ethanol has many uses that do not involve its consumption. 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.[110][111]

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). If azeotropic distillation is used to remove water, it will contain trace amounts of the material separation agent (e.g. benzene).[112] Absolute alcohol is not intended for human consumption. 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.[113]

Pure ethanol is classed as 200 proof in the US, equivalent to 175 degrees proof in the UK system.[114]

Rectified spirit, an azeotropic composition of 96% ethanol containing 4% water, is used instead of anhydrous ethanol for various purposes. Spirits of wine are about 94% ethanol (188 proof). The impurities are different from those in 95% (190 proof) laboratory ethanol.[115]

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.

In the presence of acid catalysts, alcohols can be converted to alkenes such as ethanol to ethylene. Typically solid acids such as alumina are used.[116]

   CH₃CH₂OH → H₂C=CH₂ + H₂O

Since water is removed from the same molecule, the reaction is known as intramolecular dehydration. Intramolecular dehydration of an alcohol requires a high temperature and the presence of an acid catalyst such as sulphuric acid.[117]

Ethylene produced from sugar-derived ethanol (primarily in Brazil) competes with ethylene produced from petrochemical feedstocks such as naphtha and ethane.

At a lower temperature than that of intramolecular dehydration, intermolecular alcohol dehydration may occur producing a symmetrical ether. This is a condensation reaction. In the following example, diethyl ether is produced from ethanol:

2 CH₃CH₂OH → CH₃CH₂OCH₂CH₃ + H₂O[118]

Complete combustion of ethanol forms carbon dioxide and water:

C₂H₅OH (l) + 3 O₂ (g) → 2 CO₂ (g) + 3 H₂O (l); −ΔH_c = 1371 kJ/mol[119] = 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[120]

Specific heat = 2.44 kJ/(kg·K)

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:[73]

2 CH₃CH₂OH + 2 Na → 2 CH₃CH₂ONa + H₂

or a very strong base such as sodium hydride:

CH₃CH₂OH + NaH → CH₃CH₂ONa + H₂

The acidities 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 equilibrium that is closely balanced:

CH₃CH₂OH + NaOH ⇌ CH₃CH₂ONa + H₂O

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.[102] HBr requires refluxing with a sulfuric acid catalyst.[102] Ethyl halides can, in principle, also be produced by treating ethanol with more specialized halogenating agents, such as thionyl chloride or phosphorus tribromide.[73][102]

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.[121] " An intermediate in the reaction with chlorine is the aldehyde called chloral, which forms chloral hydrate upon reaction with water:[122]

4 Cl₂ + CH₃CH₂OH → CCl₃CHO + 5 HCl

CCl₃CHO + H₂O → CCl₃C(OH)₂H

Ethanol can be oxidized to acetaldehyde and further oxidized to acetic acid, depending on the reagents and conditions.[102] 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.

Ethanol is similar to macronutrients such as proteins, fats, and carbohydrates in that it provides calories. When consumed and metabolized, it contributes 7 calories per gram via ethanol metabolism.[123]