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ETHANOIC ACID

Ethanoic acid, CH3COOH, also known as acetic acid, is an organic acid that gives vinegar its sour taste and pungent smell. It is a weak acid, in that it is only a partially dissociated acid in an aqueous solution. Pure, water-free acetic acid (glacial acetic acid) is a colorless liquid that absorbs water from the environment (hygroscopy), and freezes at 16.5 °C (62 °F) to a colorless crystalline solid. The pure acid and its concentrated solutions are dangerously corrosive. Acetic acid is one of the simplest carboxylic acids. It is an important chemical reagent and industrial chemical, used in the production of polyethylene terephthalate mainly used in soft drink bottles; cellulose acetate, mainly for photographic film; and polyvinyl acetate for wood glue, as well as synthetic fibers and fabrics. In households, diluted acetic acid is often used in descaling agents. In the food industry, acetic acid is used under the food additive code E260 as an acidity regulator and as a condiment. The global demand of acetic acid is around 6.5 million tonnes per year (Mt/a), of which approximately 1.5 Mt/a is met by recycling; the remainder is manufactured from petrochemical feedstocks or from biological sources. Dilute acetic acid produced by natural fermentation is called vinegar.

a green mixture of copper salts including copper(II) acetate. most glacial acetic acid was obtained from the "pyroligneous liquor" from distillation of wood. The acetic acid was isolated from this by treatment with milk of lime. In the 8th century. By 1910. . a sweet substance also called sugar of lead or sugar of Saturn. and the resultant calcium acetate was then acidified with sulfuric acid to recover acetic acid. The use of acetic acid in alchemy extends into the third century BC. Jabir Ibn Hayyan (Geber) was the first to concentrate acetic acid from vinegar through distillation. This reaction sequence consisted ofchlorination of carbon disulfide to carbon tetrachloride. including white lead (lead carbonate) and verdigris. In 1847 German chemist Hermann Kolbe synthesized acetic acid from inorganic materials for the first time. Germany was producing 10. The 16th-century Germanalchemist Andreas Libavius described such a procedure. Ancient Romans boiled soured wine in lead pots to produce a highly sweet syrup called sapa. and he compared the glacial acetic acid produced by this means to vinegar. French chemist Pierre Adet proved them to be identical. around 30% of which was used for the manufacture of indigo dye. At that time.HISTORY Vinegar was known early in civilization as the natural result of air exposure of beer and wine. glacial acetic acid was prepared through the dry distillation of certain metal acetates (the most noticeable one being copper(II) acetate). and concluded with electrolytic reduction to acetic acid. In the Renaissance. followed by pyrolysis to tetrachloroethylene and aqueous chlorination to trichloroacetic acid. when the Greek philosopher Theophrastus described how vinegar acted on metals to produce pigments useful in art. Sapa was rich in lead acetate. The presence of water in vinegar has such a profound effect on acetic acid's properties that for centuries chemists believed that glacial acetic acid and the acid found in vinegar were two different substances. as acetic acid-producing bacteria are present globally.000 tons of glacial acetic acid. which contributed to lead poisoning among the Roman aristocracy.

This dissolving property and miscibility of acetic acid makes it a widely used industrial chemical. and the dissociation entropy at 154± 157 J molí1 Kí1. Acetic acid is a weak. but also non-polar compounds such as oils and elements such as sulfur and iodine. and hexane. It readily mixes with other polar and non-polar solvents such as water. chloroform. and a certain extent in pure acetic acid. The dissociation enthalpy of the dimer is estimated at 65. The dimers can also be detected in the vapor at 120 °C.4. With a moderate relative static permittivity (dielectric constant) of 6. A 1. similar to ethanol and water. Cyclic dimer of acetic acid. with a pKa value of 4.CHEMICAL PROPERTIES The hydrogen (H) atom in the carboxyl group (íCOOH) in carboxylic acids such as acetic acid can be given off as an H+ ion (proton). Its conjugate base is acetate (CH3COOí). They also occur in the liquid phase in dilute solutions in nonhydrogen-bonding solvents. . giving them their acidic character. This dimerization behavior is shared by other lower carboxylic acids.0 M solution (about the concentration of domestic vinegar) has a pH of 2. dashed lines represent hydrogen bonds The crystal structure of acetic acid shows that the molecules pair up into dimers connected by hydrogen bonds. Liquid acetic acid is a hydrophilic (polar) protic solvent.0 kJ/mol. it can dissolve not only polar compounds such as inorganic salts and sugars. but are disrupted by hydrogen-bonding solvents.75. indicating that merely 0.4% of the acetic acid molecules are dissociated.2.0±66. effectively monoprotic acid in aqueous solution. and its miscibility continues to decline with longer n-alkanes. With higher alkanes (starting with octane) acetic acid is not completely miscible anymore.

which can be detected by its malodorous vapors. when exposed to oxygen.Chemical reactions Acetic acid is corrosive to metals including iron. allowing aluminum tanks to transport acetic acid. and formation of derivatives such as acetyl chloride via nucleophilic acyl substitution. With the notable exception of chromium(II) acetate. acetic acid decomposes to produce carbon dioxide and methane. A color reaction for salts of acetic acid is iron(III) chloride solution. Esters of acetic acid can likewise be formed via Fischer esterification. Acetates when heated with arsenic trioxide form cacodyl oxide. almost all acetates are soluble in water. Most notable of all its reactions is the formation of ethanol by reduction. this anhydride is produced by loss of water from two molecules of acetic acid. Metal acetates can also be prepared from acetic acid and an appropriate base. forming hydrogen gas and metal salts called acetates. Other substitution derivatives include acetic anhydride. producing a metal ethanoate when reacted with a metal. water. magnesium. Mg(s) + 2 CH3COOH(aq) (CH3COO)2Mg(aq) + H2(g) CH3COONa(aq) + CO2(g) + H2O(l) NaHCO3(s) + CH3COOH(aq) Acetic acid undergoes the typical chemical reactions of a carboxylic acid. . which results in a deeply red color that disappears after acidification. forms a thin layer of aluminum oxide on its surface. and producing a metal ethanoate. and amides can also be formed. such as producing water and a metal ethanoate when reacting with alkalis. Acetic acid can be detected by its characteristic smell. and carbon dioxide when reacting with carbonates and hydrogencarbonates. Aluminum. as in the popular "baking soda + vinegar" reaction. which is relatively resistant to the acid. and zinc. When heated above 440 °C. or to produce ethenone and water.

the artificial triglyceride triacetin (glycerin triacetate) is a common food additive. Unlike longer-chain carboxylic acids (the fatty acids).BIOCHEMISTRY The acetyl group. acetic acid does not occur in natural triglycerides. it is central to the metabolism of carbohydrates and fats. and acetic acid is produced naturally as fruits and other foods spoil. However. and is found in cosmetics and topical medicines. derived from acetic acid. When bound to coenzyme A. Acetic acid is produced and excreted by acetic acid bacteria. Acetic acid is also a component of the vaginal lubrication of humans and other primates. . and soil. the concentration of free acetic acid in cells is kept at a low level to avoid disrupting the control of the pH of the cell contents. notable ones being the Acetobacter genus and Clostridium acetobutylicum. These bacteria are found universally in foodstuffs. water. is fundamental to the biochemistry of all forms of life. where it appears to serve as a mild antibacterial agent. However.

the biological route accounts for only about 10% of world production. Alternative methods account for the rest. The two biggest producers of virgin acetic acid are Celanese and BP Chemicals. explained below.7 Mt/a is produced in Japan.PRODUCTION Acetic acid is produced both synthetically and by bacterial fermentation. Other major producers include Millennium Chemicals. Total worldwide production of virgin acetic acid is estimated at 5 Mt/a (million tonnes per year).5 Mt/a.European production stands at approximately 1 Mt/a and is declining. Today.5 Mt are recycled each year. as many nations' food purity laws stipulate that vinegar used in foods must be of biological origin. and 0. bringing the total world market to 6. Samsung. . and Svensk Etanolkemi. Eastman. About 75% of acetic acid made for use in the chemical industry is made by methanol carbonylation. Sterling Chemicals. approximately half of which is produced in the United States. but it remains important for vinegar production. Another 1.

1. CH3OH + HI CH3I + CO CH3I + H2O CH3COI CH3COOH + HI CH3COI + H2O By altering the process conditions. The first plant using this catalyst was built by US chemical company Monsanto Company in 1970. and occurs in three steps. which is promoted by ruthenium. 3. which used a cobalt catalyst. Henry Drefyus at British Celanese developed a methanol carbonylation pilot plant as early as 1925. acetic anhydride may also be produced on the same plant. In this process. often in the same production plants. methanol carbonylation long appeared to be an attractive method for acetic acid production.Methanol carbonylation Most virgin acetic acid is produced by methanol carbonylation. a lack of practical materials that could contain the corrosive reaction mixture at the high pressures needed (200 atm or more) discouraged commercialization of these routes. Because both methanol and carbon monoxide are commodity raw materials. A catalyst. the chemicals company BP Chemicals commercialized the Cativa catalyst ([Ir(CO)2I2] ). is needed for the carbonylation (step 2). The first commercial methanol carbonylation process. and rhodium-catalyzed methanol carbonylation became the dominant method of acetic acid production (see Monsanto process). methanol and carbon monoxide react to produce acetic acid according to the chemical equation: CH3OH + CO CH3COOH The process involves iodomethane as an intermediate. 2. However. was developed by German chemical company BASF in 1963. In 1968. a rhodium-based catalyst (cisí[Rh(CO)2I2] ) was discovered that could operate efficiently at lower pressure with almost no by-products. usually a metal complex. In the late 1990s. This iridiumcatalyzed Cativa process is greener and more efficient and has largely supplanted the Monsanto process. í í .

However. acetaldehyde can be oxidized by the oxygen in air to produce acetic acid 2 CH3CHO + O2 2 CH3COOH Using modern catalysts. . depending on the local price of ethylene. or by hydration of ethylene. formic acid. The acetaldehyde may be produced via oxidation of butane or light naphtha. all of which have lower boiling pointsthan acetic acid and are readily separated by distillation. including butanone. which opened an ethylene oxidation plant in ita. and chromium. cobalt. although it is uncompetitive with methanol carbonylation. Under similar conditions and using similar catalysts as are used for butane oxidation. It is thought to be competitive with methanol carbonylation for smaller plants (100±250 kt/a). formic acid. Typical reaction conditions are 150 °C and 55 atm. This remains the second-most-important manufacturing method. ethyl acetate. In more recent times. When butane or light naphtha is heated with air in the presence of various metal ions. and formaldehyde. These side-products are also commercially valuable. the separation of acetic acid from these by-products adds to the cost of the process. and the reaction conditions may be altered to produce more of them where needed. and then oxidized as above. a cheaper. this reaction can have an acetic acid yield greater than 95%. peroxides form and then decompose to produce acetic acid according to the chemical equation 2 C4H10 + 5 O2 4 CH3COOH + 2 H2O The typical reaction is run at a combination of temperature and pressure designed to be as hot as possible while still keeping the butane a liquid. The process is catalyzed by a palladium metal catalyst supported on aheteropoly acid such as tungstosilicic acid. and propionic acid. Japan. most acetic acid was produced by oxidation of acetaldehyde. in 1997. including those of manganese.Acetaldehyde oxidation Prior to the commercialization of the Monsanto process. Ethylene oxidation Acetaldehyde may be prepared from ethylene via the Wacker process. single-stage conversion of ethylene to acetic acid was commercialized by chemical company Showa Denko. The major side-products are ethyl acetate. Side-products may also form.

. and sanitary purposes increased. and not always successful. first practiced in Germany in 1823. rice. In this process. even 20% in 60-hour fed-batch process. vintners quickly learned to use other organic materials to produce vinegar in the hot summer months before the grapes were ripe and ready for processing into wine. medical. Using modern applications of this method. Commonly used feeds include apple cider. and fresh air supplied from the bottom by either natural or forced convection. acetobacter will overwhelm the yeast naturally occurring on the grapes. these bacteria can produce vinegar from a variety of alcoholic foodstuffs. vinegar of 15% acetic acid can be prepared in only 24 hours in batch process. alcohol is fermented to vinegar in a continuously stirred tank. In this method. As the demand for vinegar for culinary. wine. has been made by acetic acid bacteria of the genus Acetobacter. however. malt. The first batches of vinegar produced by fermentation probably followed errors in the winemaking process. This method was slow. first described in 1949 by Otto Hromatka and Heinrich Ebner. Nowadays. or potato mashes. airy place will become vinegar over the course of a few months. Given sufficient oxygen. The overall chemical reaction facilitated by these bacteria is: C2H5OH + O2 CH3COOH + H2O A dilute alcohol solution inoculated with Acetobacter and kept in a warm. most vinegar is made in submerged tank culture. in the form of vinegar. and fermented grain.Oxidative fermentation For most of human history. Industrial vinegar-making methods accelerate this process by improving the supply of oxygen to the bacteria. If must is fermented at too high a temperature. One of the first modern commercial processes was the "fast method" or "German method". The alcoholcontaining feed is trickled into the top of the tower. and oxygen is supplied by bubbling air through the solution. fermentation takes place in a tower packed with wood shavings or charcoal. acetic acid. as the vintners did not understand the process. The improved air supply in this process cut the time to prepare vinegar from months to weeks.

As a result. Clostridium bacteria are less acid-tolerant than Acetobacter. . including members of the genus Clostridium. although acetogenic bacteria have been known since 1940. carbon monoxide. it remains more cost-effective to produce vinegar using Acetobacter than to produce it using Clostridiumand then concentrating it. or to produce acetic acid from less costly inputs. or a mixture of carbon dioxide and hydrogen: 2 CO2 + 4 H2 CH3COOH + 2 H2O This ability of Clostridium to utilize sugars directly. their industrial use remains confined to a few niche applications.Anaerobic fermentation Species of anaerobic bacteria. compared to Acetobacter strains that can produce vinegar of up to 20% acetic acid. these acetogenic bacteria can produce acetic acid from one-carbon compounds. can convert sugars to acetic acid directly. However. including methanol. means that these bacteria could potentially produce acetic acid more efficiently than ethanol-oxidizers like Acetobacter. without using ethanol as an intermediate. from the point of view of an industrial chemist. Even the most acid-tolerant Clostridium strains can produce vinegar of only a few percent acetic acid. At present. The overall chemical reaction conducted by these bacteria may be represented as: C6H12O6 3 CH3COOH It is interesting to note that.

acrylic lacquers. The largest single use of acetic acid is in the production of vinyl acetate monomer. They are typically produced by catalyzed reaction from acetic acid and the corresponding alcohol: H3C-COOH + HO-R H3C-CO-O-R + H2O. are produced from acetaldehyde using the Tishchenko reaction. and wood stains. The three major products are ethylene glycol monoethyl ether acetate (EEA). for example EEA. This application consumes approximately 40% to 45% of the world's production of acetic acid. which are applied in paints and adhesives. ethylene glycol monobutyl ether acetate (EBA). First. closely followed by acetic anhydride and ester production.APPLICATIONS Acetic acid is a chemical reagent for the production of chemical compounds. (R = a general alkyl group) Most acetate esters. glycol monoethers are produced from ethylene oxide or propylene oxide with alcohol. The reaction is of ethylene and acetic acid with oxygen over a palladium catalyst. The esters include ethyl acetate. however. varnish removers. Ester production The major esters of acetic acid are commonly used solvents for inks. paints and coatings. In addition. n-butyl acetate. and propyl acetate. and propylene glycol monomethyl ether acetate (PMA). This application consumes about 15% to 20% of worldwide acetic acid. Ether acetates. have been shown to be harmful to human reproduction. . Vinyl acetate monomer The major use of acetic acid is for the production of vinyl acetate monomer (VAM). 2 H3C-COOH + 2 C2H4 + O2 2 H3C-CO-O-CH=CH2 + 2 H2O Vinyl acetate can be polymerized to polyvinyl acetate or to other polymers. which are then esterified with acetic acid. ether acetates are used as solvents fornitrocellulose. isobutyl acetate. The volume of acetic acid used in vinegar is comparatively small.

while commercial food pickling. In 2006. such as Friedel-Crafts alkylation. Acetic anhydride may be produced directly by methanol carbonylation bypassing the acid. with the percentage usually calculated by mass) are used directly as a condiment. Vinegar In the form of vinegar. and also in the pickling of vegetables and other foods. a synthetic textile also used for photographic film. here acetic acid acts both as a solvent and as a nucleophile to trap the rearranged carbocation. and Cativa production plants can be adapted for anhydride production. It then can be titrated using a solution in glacial acetic acid of a very strong acid. It is frequently used as a solvent for recrystallization to purify organic compounds. about 20% of acetic acid is used for TPA production. As such. Table vinegar tends to be more diluted (4% to 8% acetic acid). employs more concentrated solutions. so the amide behaves as a strong base in this medium. Acetic acid is the solvent of choice when reducing an aryl nitro-group to aniline using palladium-on-carbon. Use as solvent Glacial acetic acid is an excellent polar protic solvent. Glacial acetic acid is a much weaker base than water. Acetic anhydride is also a reagent for the production of aspirin. The amount of acetic acid used as vinegar on a worldwide scale is not large. . in general. acetic acid solutions (typically 4% to 18% acetic acid. The worldwide production of acetic anhydride is a major application. Glacial acetic acid is used in analytical chemistry for the estimation of weakly alkaline substances such as organic amides. For example. its major application is for cellulose acetate. such as perchloric acid. heroin. Pure acetic acid is used as a solvent in the production of terephthalic acid (TPA). one stage in the commercial manufacture of synthetic camphor involves aWagner-Meerwein rearrangement of camphene to isobornyl acetate. and uses approximately 25% to 30% of the global production of acetic acid. Acetic anhydride is a strong acetylation agent. but is by far the oldest and best-known application. Acetic acid is often used as a solvent for reactions involving carbocations. and other compounds. the raw material for polyethylene terephthalate (PET).Acetic anhydride The condensation product of two molecules of acetic acid is acetic anhydride. as noted above.

In this manner.         Bromoacetic acid. Examples in the household environment include the use in a stop bath during the development of photographic films. dichloroacetic acid (considered a by-product). however. Palladium(II) acetate. Organic or inorganic salts are produced from acetic acid. Silver acetate. MCA is used in the manufacture of indigo dye.Other applications Dilute solutions of acetic acids are also used for their mild acidity. These applications are. Glacial acetic acid is also used as a wart and verruca remover. Copper(II) acetate. and trichloroacetic acid. and for treating outer ear infectionsin people in preparations such as Vosol. Trifluoroacetic acid. acetic acid is used as a spray-on preservative for livestock silage. Diluted acetic acid is also used in physical therapy to break up nodules of scar tissue via iontophoresis. not expected to grow as much as TPA production. used as a catalyst for organic coupling reactions such as the Heck reaction. The acidity is also used for treating the sting of the box jellyfish by disabling the stinging cells of the jellyfish. used as a pesticide. and in descaling agents to remove limescale from taps and kettles. which can obscure other important constituents in urine during a microscopic examination. Dilute solutions of glacial acetic acid can be used in the clinical laboratory to lyse red blood cells in order to do manual white blood cell counts. including: Sodium acetate. . which is esterified to produce the reagent ethyl bromoacetate. Substituted acetic acids produced include: Monochloroacetic acid (MCA). to discourage bacterial and fungal growth. Aluminium acetate and iron(II) acetate²used as mordants for dyes. preventing serious injury or death if applied immediately. Amounts of acetic acid used in these other applications together (apart from TPA) account for another 5±10% of acetic acid use worldwide. which is a common reagent in organic synthesis. used as a pigment and a fungicide. Another clinical use is for lysing red blood cells. used in the textile industry and as a food preservative (E262).

SAFETY Concentrated acetic acid is corrosive and must. The following table lists the EU classification of bacetic acid solutions: Concentration by weight Molarity Classification R-Phrases 10±25% 1. Due to incompatibilities.4±16%). It can cause severe damage to the digestive system. it is recommended to keep acetic acid away from chromic acid. perchloric acid. permanent eye damage. so specially resistant gloves. Dilute acetic acid. since it can cause skin burns.67±4.16 mol/L Irritant (Xi) R36/38 25±90% 4.16±14. These burns or blisters may not appear until hours after exposure.99 mol/L Corrosive (C) Flammable (F) R10. R35 Solutions at more than 25% acetic acid are handled in a fume hood because of the pungent. It becomes a flammable risk if the ambient temperature exceeds 39 °C (102 °F). are worn when handling the compound.99 mol/L Corrosive (C) R34 >90% >14. such as those made of nitrile rubber. However. and irritation to the mucous membranes. therefore. . ethylene glycol. ingestion of stronger solutions is dangerous to human and animal life. is harmless. permanganates.peroxides and hydroxyls. Concentrated acetic acid can be ignited with difficulty in the laboratory. and can form explosive mixtures with air above this temperature (explosive limits: 5. nitric acid. in the form of vinegar. be handled with appropriate care. The hazards of solutions of acetic acid depend on the concentration. and a potentially lethal change in the acidity of the blood. corrosive vapor. Latex gloves offer no protection.