Acetic acid, also known as ethanoic acid, is an organic chemical compound best recognized for giving vinegar its sour taste and pungent smell. Pure water-free acetic acid (glacial acetic acid) is a colorless hygroscopic liquid and freezes below 16.7°C (62°F) to a colourless crystalline solid. Acetic acid is corrosive, and its vapour is irritating to eyes and nose, although it is a weak acid based on its ability to dissociate in aqueous solutions.

Acetic acid is one of the simplest carboxylic acids (the second-simplest, next to formic acid). It is an important chemical reagent and industrial chemical that is 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 many synthetic fibres 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.

Nomenclature

Acetic acid has the empirical formula CH₂O and the molecular formula C₂H₄O₂. The latter is often written as CH₃-COOH, CH₃COOH, or CH₃CO₂H to better reflect its structure. The ion resulting from loss of H⁺ from acetic acid is the acetate anion. The name acetate can also refer to a salt containing this anion or an ester of acetic acid.

History

Acetic acid-producing bacteria are present throughout the world, and any culture practicing the brewing of beer or wine inevitably discovered vinegar as the natural result of these alcoholic beverages being exposed to air. The use of acetic acid in chemistry extends into antiquity. In the 3rd century BC, the Greek philosopher Theophrastos described how vinegar acted on metals to produce pigments useful in art, including white lead (lead carbonate) and verdigris, a green mixture of copper salts including copper(II) acetate. Ancient Romans boiled soured wine in lead pots to produce a highly sweet syrup called sapa. Sapa was rich in lead acetate, a sweet substance also called sugar of lead or sugar of Saturn, which contributed to lead poisoning among the Roman aristocracy. The 8th century Persian alchemist Jabir Ibn Hayyan (Geber) concentrated acetic acid from vinegar through distillation. In the Renaissance, glacial acetic acid was prepared through the dry distillation of metal acetates. The 16th century German alchemist Andreas Libavius described such a procedure, and he compared the glacial acetic acid produced by this means to vinegar. The presence of water in vinegar has such a profound effect on acetic acid's properties that for centuries many chemists believed that glacial acetic acid and the acid found in vinegar were two different substances. The French chemist Pierre Adet proved them to be identical. In 1847 the German chemist Hermann Kolbe synthesised acetic acid from inorganic materials for the first time. This reaction sequence consisted of chlorination of carbon disulfide to carbon tetrachloride, followed by pyrolysis to tetrachloroethylene and aqueous chlorination to trichloroacetic acid, and concluded with electrolytic reduction to acetic acid.^[1]By 1910 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, and the resultant calcium acetate was then acidified with sulfuric acid to recover acetic acid. At this time Germany was producing 10,000 tons of glacial acetic acid, around 30% of which was used for the manufacture of indigo dye.^[2][3]

Chemical properties

Acidity

The hydrogen (H) atom in the carboxyl group (−COOH) in carboxylic acids such as acetic acid can be given off as an H⁺ ion (proton), giving them their acidic character. Acetic acid is a weak, effectively monoprotic acid in aqueous solution, with a pK_a value of 4.8. A 1.0 M solution (about the concentration of domestic vinegar) has a pH of 2.4, indicating that merely 0.4% of the acetic acid molecules are dissociated.

The crystal structure of acetic acid^[4] shows that the molecules pair up into dimers connected by hydrogen bonds. The dimers can also be detected in the vapour at 120 Â°C. They probably also occur in the liquid phase of pure acetic acid, but are rapidly disrupted if any water is present. This dimerisation behaviour is shared by other lower carboxylic acids.

Solvent

Liquid acetic acid is a hydrophilic (polar) protic solvent, similar to ethanol and water. With a moderate dielectric constant of 6.2, it can dissolve not only polar compounds such as inorganic salts and sugars, but also non-polar compounds such as oils and elements such as sulfur and iodine. It readily mixes with many other polar and non-polar solvents such as water, chloroform, and hexane. This dissolving property and miscibility of acetic acid makes it a widely used industrial chemical.

Detection

Acetic acid can be detected by its characteristic smell. A colour reaction for salts of acetic acid is iron(III) chloride solution, which results in a deeply red colour that disappears after acidification. Acetates when heated with arsenic trioxide form cacodyl oxide, which can be detected by its malodorous vapours.

Production

Acetic acid is produced both synthetically and by bacterial fermentation. Today, the biological route accounts for only about 10% of world production, but it remains important for vinegar production, as many of the world food purity laws stipulate that vinegar used in foods must be of biological origin. About 75% of acetic acid made for use in the chemical industry is made by methanol carbonylation, explained below. Alternative methods account for the rest.^[6]

Total worldwide production of virgin acetic acid is estimated at 5 Mt/a (million tonnes per year), approximately half of which is produced in the United States. European production stands at approximately 1 Mt/a and is declining, and 0.7 Mt/a is produced in Japan. Another 1.5 Mt are recycled each year, bringing the total world market to 6.5 Mt/a.^[7][8] The two biggest producers of virgin acetic acid are Celanese and BP Chemicals. Other major producers include Millennium Chemicals, Sterling Chemicals, Samsung, Eastman, and Svensk Etanolkemi.

Fermentation

Oxidative fermentation

For most of human history, acetic acid, in the form of vinegar, has been made by bacteria of the genus Acetobacter. Given sufficient oxygen, these bacteria can produce vinegar from a variety of alcoholic foodstuffs. Commonly used feeds include apple cider, wine, and fermented grain, malt, rice, or potato mashes. 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, airy place will become vinegar over the course of a few months. Industrial vinegar-making methods accelerate this process by improving the supply of oxygen to the bacteria.

The first batches of vinegar produced by fermentation probably followed errors in the winemaking process. If must is fermented at too high a temperature, acetobacter will overwhelm the yeast naturally occurring on the grapes. As the demand for vinegar for culinary, medical, and sanitary purposes increased, 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. This method was slow, however, and not always successful, as the vintners did not understand the process.

Vinegar

In the form of vinegar, acetic acid solutions (typically 5% to 18% acetic acid, with the percentage usually calculated by mass) are used directly as a condiment, and also in the pickling of vegetables and other foodstuffs. Table vinegar tends to be more dilute (5% to 8% acetic acid), while commercial food pickling generally employs more concentrated solutions. The amount of acetic aid used as vinegar on a worldwide scale is not large, but historically, this is by far the oldest and most well-known application.

References

External links

• CID 176 from PubChem
• Computational Chemistry Wiki
• International Chemical Safety Card 0363
• Acetic acid MSDS (Material Safety Data Sheet)
• National Pollutant Inventory - Acetic acid fact sheet
• NIOSH Pocket Guide to Chemical Hazards
• 29 CFR 1910.1000, Table Z-1 (US Permissible exposure limits)
• Occupational Training NFPA tables
• Celanese, major acetic acid producer
• Usage of acetic acid in Organic Syntheses
• Acetic acid pH and titration - freeware for data analysis, simulation and distribution diagram generation

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