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.

Vinegar was known early in civilization as the natural result of air exposure of beer and wine, as acetic acid-producing

bacteria are present globally. The use of acetic acid in alchemy extends into the third century BC, when

the Greek philosopher Theophrastus 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.

In the 8th century, Jabir Ibn Hayyan (Geber) was the first to concentrate acetic acid from vinegar through distillation.

In the Renaissance, glacial acetic acid was prepared through the dry distillation of certain metal acetates (the most

noticeable one being copper(II) acetate). The 16th-century Germanalchemist 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 chemists believed that glacial acetic

acid and the acid found in vinegar were two different substances. French chemist Pierre Adet proved them to be

identical.

In 1847 German chemist Hermann Kolbe synthesized acetic acid from inorganic materials for the first time. This

reaction sequence consisted ofchlorination 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.

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 that time, Germany was producing 10,000 tons of glacial acetic acid,

around 30% of which was used for the manufacture of indigo dye.
CHEMICAL PROPERTIES

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 pKa value of 4.75. Its conjugate base is acetate (CH3COO−). 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.

Cyclic dimer of acetic acid; dashed lines represent hydrogen bonds

The crystal structure of acetic acid shows that the molecules pair up into dimers connected by hydrogen bonds. The

dimers can also be detected in the vapor at 120 °C. They also occur in the liquid phase in dilute solutions in non-

hydrogen-bonding solvents, and a certain extent in pure acetic acid, but are disrupted by hydrogen-bonding solvents.

The dissociation enthalpy of the dimer is estimated at 65.0–66.0 kJ/mol, and the dissociation entropy at 154–

157 J mol−1 K−1. This dimerization behavior is shared by other lower carboxylic acids.

Liquid acetic acid is a hydrophilic (polar) protic solvent, similar to ethanol and water. With a moderate relative static

permittivity (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 other polar

and non-polar solvents such as water, chloroform, and hexane. With higher alkanes (starting with octane) acetic acid

is not completely miscible anymore, and its miscibility continues to decline with longer n-alkanes. This dissolving

property and miscibility of acetic acid makes it a widely used industrial chemical.

Acetic acid is corrosive to metals including iron, magnesium, and zinc, forming hydrogen gas and metal salts called

acetates. Aluminum, when exposed to oxygen, forms a thin layer of aluminum oxide on its surface, which is relatively

resistant to the acid, allowing aluminum tanks to transport acetic acid. Metal acetates can also be prepared from

acetic acid and an appropriate base, as in the popular "baking soda + vinegar" reaction. With the notable exception

of chromium(II) acetate, almost all acetates are soluble in water.

Mg(s) + 2 CH3COOH(aq) → (CH3COO)2Mg(aq) + H2(g)

NaHCO3(s) + CH3COOH(aq) → CH3COONa(aq) + CO2(g) + H2O(l)

Acetic acid undergoes the typical chemical reactions of a carboxylic acid, such as producing water and a

metal ethanoate when reacting with alkalis, producing a metal ethanoate when reacted with a metal, and producing a

metal ethanoate, water, and carbon dioxide when reacting with carbonates and hydrogencarbonates. Most notable of

all its reactions is the formation of ethanol by reduction, and formation of derivatives such as acetyl

chloride via nucleophilic acyl substitution. Other substitution derivatives include acetic anhydride; this anhydride is

produced by loss of water from two molecules of acetic acid. Esters of acetic acid can likewise be formed via Fischer

esterification, and amides can also be formed. When heated above 440 °C, acetic acid decomposes to

produce carbon dioxide and methane, or to produce ethenone and water.

Acetic acid can be detected by its characteristic smell. A color reaction for salts of acetic acid is iron(III)

chloride solution, which results in a deeply red color that disappears after acidification. Acetates when heated

with arsenic trioxide form cacodyl oxide, which can be detected by its malodorous vapors.

The acetyl group, derived from acetic acid, is fundamental to the biochemistry of all forms of life. When bound

to coenzyme A, it is central to the metabolism of carbohydrates and fats. However, 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. Unlike longer-chain

carboxylic acids (the fatty acids), acetic acid does not occur in natural triglycerides. However, the artificial

triglyceride triacetin (glycerin triacetate) is a common food additive, and is found in cosmetics and topical medicines.

Acetic acid is produced and excreted by acetic acid bacteria, notable ones being the Acetobacter genus

and Clostridium acetobutylicum. These bacteria are found universally in foodstuffs, water, and soil, and acetic acid is

produced naturally as fruits and other foods spoil. Acetic acid is also a component of the vaginal

lubrication of humans and other primates, where it appears to serve as a mild antibacterial agent.

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 nations' 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.

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. 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.

Most virgin acetic acid is produced by methanol carbonylation. In this 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, and occurs in three steps. A catalyst, usually a

metal complex, is needed for the carbonylation (step 2).

1. CH3OH + HI → CH3I + H2O

2. CH3I + CO → CH3COI

3. CH3COI + H2O → CH3COOH + HI

By altering the process conditions, acetic anhydride may also be produced on the same plant. Because both

methanol and carbon monoxide are commodity raw materials, methanol carbonylation long appeared to be an

attractive method for acetic acid production. Henry Drefyus at British Celanese developed a methanol carbonylation

pilot plant as early as 1925. However, 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. The first commercial

methanol carbonylation process, which used a cobalt catalyst, was developed by German chemical

company BASF in 1963. In 1968, a rhodium-based catalyst (cis−[Rh(CO)2I2]−) was discovered that could operate

efficiently at lower pressure with almost no by-products. The first plant using this catalyst was built by US chemical

company Monsanto Company in 1970, and rhodium-catalyzed methanol carbonylation became the dominant method

of acetic acid production (see Monsanto process). In the late 1990s, the chemicals company BP

Chemicals commercialized the Cativa catalyst ([Ir(CO)2I2]−), which is promoted by ruthenium. This iridium-

catalyzed Cativa process is greener and more efficient and has largely supplanted the Monsanto process, often in the

same production plants.

Prior to the commercialization of the Monsanto process, most acetic acid was produced by oxidation of acetaldehyde.

This remains the second-most-important manufacturing method, although it is uncompetitive with methanol

carbonylation.

The acetaldehyde may be produced via oxidation of butane or light naphtha, or by hydration of ethylene.

When butane or light naphtha is heated with air in the presence of various metal ions, including those

of manganese, cobalt, and chromium, 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. Typical reaction conditions are 150 °C and 55 atm. Side-products may also form,

including butanone, ethyl acetate, formic acid, and propionic acid. These side-products are also commercially

valuable, and the reaction conditions may be altered to produce more of them where needed. However, the

separation of acetic acid from these by-products adds to the cost of the process.

Under similar conditions and using similar catalysts as are used for butane oxidation, acetaldehyde can be oxidized

by the oxygen in air to produce acetic acid

2 CH3CHO + O2 → 2 CH3COOH

Using modern catalysts, this reaction can have an acetic acid yield greater than 95%. The major side-products

are ethyl acetate, formic acid, and formaldehyde, all of which have lower boiling pointsthan acetic acid and are readily

separated by distillation.

Ethylene oxidation

Acetaldehyde may be prepared from ethylene via the Wacker process, and then oxidized as above. In more recent

times, a cheaper, single-stage conversion of ethylene to acetic acid was commercialized by chemical

company Showa Denko, which opened an ethylene oxidation plant in Ōita, Japan, in 1997. The process is catalyzed

by a palladium metal catalyst supported on aheteropoly acid such as tungstosilicic acid. It is thought to be competitive

with methanol carbonylation for smaller plants (100–250 kt/a), depending on the local price of ethylene.
Oxidative fermentation

For most of human history, acetic acid, in the form of vinegar, has been made by acetic acid 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.

One of the first modern commercial processes was the "fast method" or "German method", first practiced in Germany

in 1823. In this process, fermentation takes place in a tower packed with wood shavings or charcoal. The alcohol-

containing feed is trickled into the top of the tower, and fresh air supplied from the bottom by either natural or

forced convection. The improved air supply in this process cut the time to prepare vinegar from months to weeks.

Nowadays, most vinegar is made in submerged tank culture, first described in 1949 by Otto Hromatka and Heinrich

Ebner. In this method, alcohol is fermented to vinegar in a continuously stirred tank, and oxygen is supplied by

bubbling air through the solution. Using modern applications of this method, vinegar of 15% acetic acid can be

prepared in only 24 hours in batch process, even 20% in 60-hour fed-batch process.
Anaerobic fermentation

Species of anaerobic bacteria, including members of the genus Clostridium, can convert sugars to acetic acid

directly, without using ethanol as an intermediate. The overall chemical reaction conducted by these bacteria may be

represented as:

C6H12O6 → 3 CH3COOH

It is interesting to note that, from the point of view of an industrial chemist, these acetogenic bacteria can produce

acetic acid from one-carbon compounds, including methanol, carbon monoxide, or a mixture of carbon

dioxide and hydrogen:

2 CO2 + 4 H2 → CH3COOH + 2 H2O

This ability of Clostridium to utilize sugars directly, or to produce acetic acid from less costly inputs, means that these

bacteria could potentially produce acetic acid more efficiently than ethanol-oxidizers like Acetobacter.

However, Clostridium bacteria are less acid-tolerant than Acetobacter. Even the most acid-tolerant Clostridium strains

can produce vinegar of only a few percent acetic acid, compared to Acetobacter strains that can produce vinegar of

up to 20% acetic acid. At present, it remains more cost-effective to produce vinegar using Acetobacter than to

produce it using Clostridiumand then concentrating it. As a result, although acetogenic bacteria have been known

since 1940, their industrial use remains confined to a few niche applications.
APPLICATIONS

Acetic acid is a chemical reagent for the production of chemical compounds. The largest single use of acetic acid is in

the production of vinyl acetate monomer, closely followed by acetic anhydride and ester production. The volume of

acetic acid used in vinegar is comparatively small.

Vinyl acetate monomer

The major use of acetic acid is for the production of vinyl acetate monomer (VAM). This application consumes

approximately 40% to 45% of the world's production of acetic acid. The reaction is of ethylene and acetic acid

with oxygen over a palladium catalyst.

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 applied

in paints and adhesives.

Ester production

The major esters of acetic acid are commonly used solvents for inks, paints and coatings. The esters include ethyl

acetate, n-butyl acetate, isobutyl acetate, and propyl acetate. They are typically produced by catalyzed reaction from

acetic acid and the corresponding alcohol:

H3C-COOH + HO-R → H3C-CO-O-R + H2O, (R = a general alkyl group)

Most acetate esters, however, are produced from acetaldehyde using the Tishchenko reaction. In addition, ether

acetates are used as solvents fornitrocellulose, acrylic lacquers, varnish removers, and wood stains. First, glycol

monoethers are produced from ethylene oxide or propylene oxide with alcohol, which are then esterified with acetic

acid. The three major products are ethylene glycol monoethyl ether acetate (EEA), ethylene glycol monobutyl ether

acetate (EBA), and propylene glycol monomethyl ether acetate (PMA). This application consumes about 15% to 20%

of worldwide acetic acid. Ether acetates, for example EEA, have been shown to be harmful to human reproduction.
Acetic anhydride

The condensation product of two molecules of acetic acid is acetic anhydride. The worldwide production of acetic

anhydride is a major application, and uses approximately 25% to 30% of the global production of acetic acid. Acetic

anhydride may be produced directly by methanol carbonylation bypassing the acid, and Cativa production plants can

be adapted for anhydride production.

Acetic anhydride is a strong acetylation agent. As such, its major application is for cellulose acetate, a

synthetic textile also used for photographic film. Acetic anhydride is also a reagent for the production

of aspirin, heroin, and other compounds.

Vinegar

In the form of vinegar, acetic acid solutions (typically 4% 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 foods. Table vinegar

tends to be more diluted (4% to 8% acetic acid), while commercial food pickling, in general, employs more

concentrated solutions. The amount of acetic acid used as vinegar on a worldwide scale is not large, but is by far the

oldest and best-known application.

Use as solvent

Glacial acetic acid is an excellent polar protic solvent, as noted above. It is frequently used as a solvent

for recrystallization to purify organic compounds. Pure acetic acid is used as a solvent in the production

of terephthalic acid (TPA), the raw material for polyethylene terephthalate (PET). In 2006, about 20% of acetic acid is

used for TPA production.

Acetic acid is often used as a solvent for reactions involving carbocations, such as Friedel-Crafts alkylation. For

example, one stage in the commercial manufacture of synthetic camphor involves aWagner-Meerwein

rearrangement of camphene to isobornyl acetate; here acetic acid acts both as a solvent and as a nucleophile to trap

the rearranged carbocation. Acetic acid is the solvent of choice when reducing an aryl nitro-group

to aniline using palladium-on-carbon.

Glacial acetic acid is used in analytical chemistry for the estimation of weakly alkaline substances such as organic

amides. Glacial acetic acid is a much weaker base than water, so the amide behaves as a strong base in this

medium. It then can be titrated using a solution in glacial acetic acid of a very strong acid, such as perchloric acid.
 Other applications

Dilute solutions of acetic acids are also used for their mild acidity. Examples in the household environment include

the use in a stop bath during the development of photographic films, and in descaling agents to

remove limescale from taps and kettles.

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. Another clinical use is for lysing red blood cells, which can obscure other important

constituents in urine during a microscopic examination.

The acidity is also used for treating the sting of the box jellyfish by disabling the stinging cells of the jellyfish,

preventing serious injury or death if applied immediately, and for treating outer ear infectionsin people in preparations

such as Vosol. In this manner, acetic acid is used as a spray-on preservative for livestock silage, to discourage

bacterial and fungal growth. Glacial acetic acid is also used as a wart and verruca remover.

Organic or inorganic salts are produced from acetic acid, including:

 Sodium acetate, used in the textile industry and as a food preservative (E262).

 Copper(II) acetate, used as a pigment and a fungicide.

 Aluminium acetate and iron(II) acetate—used as mordants for dyes.

 Palladium(II) acetate, used as a catalyst for organic coupling reactions such as the Heck reaction.

 Silver acetate, used as a pesticide.

Substituted acetic acids produced include:

 Monochloroacetic acid (MCA), dichloroacetic acid (considered a by-product), and trichloroacetic acid. MCA

is used in the manufacture of indigo dye.

 Bromoacetic acid, which is esterified to produce the reagent ethyl bromoacetate.

 Trifluoroacetic acid, which is a common reagent in organic synthesis.

Amounts of acetic acid used in these other applications together (apart from TPA) account for another 5–10% of

acetic acid use worldwide. These applications are, however, not expected to grow as much as TPA

production. Diluted acetic acid is also used in physical therapy to break up nodules of scar tissue via iontophoresis.
SAFETY

Concentrated acetic acid is corrosive and must, therefore, be handled with appropriate care, since it can cause skin

burns, permanent eye damage, and irritation to the mucous membranes. These burns or blisters may not appear until

hours after exposure. Latex gloves offer no protection, so specially resistant gloves, such as those made of nitrile

rubber, are worn when handling the compound. Concentrated acetic acid can be ignited with difficulty in the

laboratory. It becomes a flammable risk if the ambient temperature exceeds 39 °C (102 °F), and can form explosive

mixtures with air above this temperature (explosive limits: 5.4–16%).

The hazards of solutions of acetic acid depend on the concentration. The following table lists the EU classification of

bacetic acid solutions:

Concentratio
n Molarity Classification R-Phrases
by weight

10–25% 1.67–4.16 mol/L Irritant (Xi) R36/38

4.16–14.99 mol/
25–90% Corrosive (C) R34
L

>90% >14.99 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, corrosive vapor. Dilute

acetic acid, in the form of vinegar, is harmless. However, ingestion of stronger solutions is dangerous to human and

animal life. It can cause severe damage to the digestive system, and a potentially lethal change in the acidity of

the blood.

Due to incompatibilities, it is recommended to keep acetic acid away from chromic acid, ethylene glycol, nitric

acid, perchloric acid, permanganates,peroxides and hydroxyls.