Formic acid, systematically named methanoic acid, is the simplest carboxylic acid, and has

the chemical formula HCOOH. The chemical composition is HCOOH. It is an important intermediate

in chemical synthesis and occurs naturally, most notably in some ants. The word "formic" comes from
the Latin word for ant, formica, referring to its early isolation by the distillation of ant
bodies. Esters, salts, and the anion derived from formic acid are called formates. Industrially, formic
acid is produced from methanol.

Contents

 1Properties
 2Natural occurrence
 3Production
o 3.1From methyl formate and formamide
o 3.2Niche chemical routes
 3.2.1By-product of acetic acid production
 3.2.2Hydrogenation of carbon dioxide
 3.2.3Oxidation of biomass
 3.2.4Laboratory methods
 3.2.5Electrochemical production
o 3.3Biosynthesis
 4Uses
 5Chemical reactions
 6Reactions
o 6.1Decomposition
o 6.2Addition to alkenes
o 6.3Formic acid anhydride
 7History
 8Safety
 9See also
 10References
 11External links

Properties[edit]

Cyclic dimer of formic acid; dashed green lines represent hydrogen bonds

Formic acid is a colorless liquid having a pungent, penetrating odor [5] at room temperature, not unlike
the related acetic acid. It is miscible with water and most polar organic solvents, and is somewhat
soluble in hydrocarbons. In hydrocarbons and in the vapor phase, it consists of hydrogen-
bonded dimers rather than individual molecules.[6][7] Owing to its tendency to hydrogen-bond, gaseous
formic acid does not obey the ideal gas law.[7] Solid formic acid, which can exist in either of
two polymorphs, consists of an effectively endless network of hydrogen-bonded formic acid
molecules. Formic acid forms a low-boiling azeotrope with water (22.4%). Liquid formic acid tends
to supercool.
Natural occurrence[edit]
See also: Insect defenses
In nature, formic acid is found in most ants and in stingless bees of the genus Oxytrigona.[8]
[9]
 The wood ants from the genus Formica can spray formic acid on their prey or to defend the nest. It
is also found in the trichomes of stinging nettle (Urtica dioica). Formic acid is a naturally occurring
component of the atmosphere primarily due to forest emissions.[10]

Production[edit]
In 2009, the worldwide capacity for producing formic acid was 720,000 tonnes per year, roughly
equally divided between Europe (350,000, mainly in Germany) and Asia (370,000, mainly in China)
while production was below 1000 tonnes per year in all other continents. [11] It is commercially available
in solutions of various concentrations between 85 and 99 w/w %.[6] As of 2009, the largest producers
are BASF, Eastman Chemical Company, LC Industrial, and Feicheng Acid Chemicals, with the
largest production facilities in Ludwigshafen (200,000 tonnes per year, BASF,
Germany), Oulu (105,000, Eastman, Finland), Nakhon Pathom (n/a, LC Industrial),
and Feicheng (100,000, Feicheng, China). 2010 prices ranged from around €650/tonne (equivalent to
around $800/tonne) in Western Europe to $1250/tonne in the United States. [11]
From methyl formate and formamide[edit]
When methanol and carbon monoxide are combined in the presence of a strong base, the result
is methyl formate, according to the chemical equation:[6]
CH3OH + CO → HCO2CH3
In industry, this reaction is performed in the liquid phase at elevated pressure. Typical reaction
conditions are 80 °C and 40 atm. The most widely used base is sodium methoxide. Hydrolysis of
the methyl formate produces formic acid:
HCO2CH3 + H2O → HCOOH + CH3OH
Efficient hydrolysis of methyl formate requires a large excess of water. Some routes proceed
indirectly by first treating the methyl formate with ammonia to give formamide, which is then
hydrolyzed with sulfuric acid:
HCO2CH3 + NH3 → HC(O)NH2 + CH3OH
2 HC(O)NH2 + 2H2O + H2SO4 → 2HCO2H + (NH4)2SO4
A disadvantage of this approach is the need to dispose of the ammonium
sulfate byproduct. This problem has led some manufacturers to develop energy-
efficient methods of separating formic acid from the excess water used in direct
hydrolysis. In one of these processes, used by BASF, the formic acid is removed from
the water by liquid-liquid extraction with an organic base.[citation needed]
Niche chemical routes[edit]
By-product of acetic acid production[edit]
A significant amount of formic acid is produced as a byproduct in the manufacture of
other chemicals. At one time, acetic acid was produced on a large scale by oxidation
of alkanes, by a process that cogenerates significant formic acid. [citation needed] This oxidative
route to acetic acid is declining in importance, so that the aforementioned dedicated
routes to formic acid have become more important.
Hydrogenation of carbon dioxide[edit]
 The catalytic hydrogenation of CO2 to formic acid has long been studied. This reaction
can be conducted homogeneously.[12][13]
Oxidation of biomass[edit]
Formic acid can also be obtained by aqueous catalytic partial oxidation of wet biomass
by the OxFA process.[14][15] A Keggin-type polyoxometalate (H5PV2Mo10O40) is used as the
homogeneous catalyst to convert sugars, wood, waste paper, or cyanobacteria to
formic acid and CO2 as the sole byproduct. Yields of up to 53% formic acid can be
achieved.[citation needed]
Laboratory methods[edit]
In the laboratory, formic acid can be obtained by heating oxalic acid in glycerol and
extraction by steam distillation.[16] Glycerol acts as a catalyst, as the reaction proceeds
through a glyceryl oxalate intermediate. If the reaction mixture is heated to higher
temperatures, allyl alcohol results. The net reaction is thus:
C2O4H2 → CO2H2 + CO2
Another illustrative method involves the reaction between lead
formate and hydrogen sulfide, driven by the formation of lead sulfide.[17]
Pb(HCOO)2 + H2S → 2HCOOH + PbS
Electrochemical production[edit]
It has been reported that formate can be formed by the electrochemical
reduction of CO
2 (in the form of bicarbonate) at a lead cathode at pH 8.6:[18]
HCO−
3 + H

2O + 2e  → HCO
- −

2 + 2OH
−

or
CO
2 + H

2O + 2e  → HCO
- −

2 + OH
−

If the feed is CO

2 and oxygen is evolved at the anode, the total reaction is:

CO
2 + OH−
 → HCO−
2 + 1/2 O2

This has been proposed as a large-scale source of formate by

various groups.[19] The formate could be used as feed to modified E.
coli bacteria for producing biomass.[20][21] There exist natural microbes
that can feed on formic acid or formate (see Methylotroph).
Biosynthesis[edit]
Formic acid is named after ants which have high concentrations of
the compound in their venom. In ants, formic acid is derived
from serine through a 5,10-methenyltetrahydrofolate intermediate.
[22]
 The conjugate base of formic acid, formate, also occurs widely in
nature. An assay for formic acid in body fluids, designed for
determination of formate after methanol poisoning, is based on the
reaction of formate with bacterial formate dehydrogenase.[23]

Uses[edit]
A major use of formic acid is as
a preservative and antibacterial agent in livestock feed. In Europe, it
is applied on silage, including fresh hay, to promote the fermentation
of lactic acid and to suppress the formation of butyric acid; it also
allows fermentation to occur quickly, and at a lower temperature,
reducing the loss of nutritional value.[6] Formic acid arrests certain
decay processes and causes the feed to retain its nutritive value
longer, and so it is widely used to preserve winter feed for cattle.[24] In
the poultry industry, it is sometimes added to feed to kill E.
coli bacteria.[25][26] Use as preservative for silage and (other) animal
feed constituted 30% of the global consumption in 2009. [11]
Formic acid is also significantly used in the production of leather,
including tanning (23% of the global consumption in 2009[11]), and in
dyeing and finishing textiles (9% of the global consumption in 2009 [11])
because of its acidic nature. Use as a coagulant in the production of
rubber[6] consumed 6% of the global production in 2009. [11]
Formic acid is also used in place of mineral acids for various
cleaning products,[6] such as limescale remover and toilet bowl
cleaner. Some formate esters are artificial flavorings and perfumes.
Beekeepers use formic acid as a miticide against the tracheal mite
(Acarapis woodi) and the Varroa destructor mite and Varroa
jacobsoni mite.[27]
Formic acid application has been reported to be an effective
treatment for warts.[28]
Formic acid can be used as a fuel cell (it can be used directly
in formic acid fuel cells and indirectly in hydrogen fuel cells). [29][30]
It is possible to use formic acid as an intermediary to produce
isobutanol from CO2 using microbes[31][32][33]
Formic acid is often used as a component of mobile phase
in reversed-phase high-performance liquid chromatography (RP-
HPLC) analysis and separation techniques for the separation of
hydrophobic macromolecules, such as peptides, proteins and more
complex structures including intact viruses. Especially when paired
with mass spectrometry detection, formic acid offers several
advantages over the more traditionally used phosphoric acid. [34][35]

Chemical reactions[edit]
Formic acid is about ten times stronger than acetic acid. It is used as
a volatile pH modifier in HPLC and capillary electrophoresis.
 Formic acid is a source for a formyl group for example in
the formylation of methylaniline to N-methylformanilide in toluene.[36]
In synthetic organic chemistry, formic acid is often used as a source
of hydride ion. The Eschweiler-Clarke reaction and the Leuckart-
Wallach reaction are examples of this application. It, or more
commonly its azeotrope with triethylamine, is also used as a source
of hydrogen in transfer hydrogenation.

As mentioned below, formic acid readily decomposes with

concentrated sulfuric acid to form carbon monoxide.
CH2O2 + H2SO4 → H2SO4 + H2O + CO

Reactions[edit]
Formic acid shares most of the chemical properties of
other carboxylic acids. Because of its high acidity, solutions in
alcohols form esters spontaneously. Formic acid shares some of
the reducing properties of aldehydes, reducing solutions of gold,
silver, and platinum to the metals.[citation needed]
Decomposition[edit]
Heat and especially acids cause formic acid to decompose
to carbon monoxide (CO) and water (dehydration). Treatment of
formic acid with sulfuric acid is a convenient laboratory source of
CO.[37][38]
In the presence of platinum, it decomposes with a release
of hydrogen and carbon dioxide.
CH2O2 → H2 + CO2
Soluble ruthenium catalysts are also effective. [39][40] Carbon
monoxide free hydrogen has been generated in a very wide
pressure range (1–600 bar).[39] Formic acid has been
considered as a means of hydrogen storage.[41] The co-
product of this decomposition, carbon dioxide, can be
rehydrogenated back to formic acid in a second step. Formic
acid contains 53 g/L hydrogen at room temperature and
atmospheric pressure, which is three and a half times as
much as compressed hydrogen gas can attain at 350 bar
pressure (14.7 g/L). Pure formic acid is a liquid with a flash
point of +69 °C, much higher than that of gasoline (−40 °C) or
ethanol (+13 °C).[citation needed]
Addition to alkenes[edit]
Formic acid is unique among the carboxylic acids in its ability
to participate in addition reactions with alkenes. Formic acids
and alkenes readily react to form formate esters. In the
presence of certain acids, including sulfuric and hydrofluoric
acids, however, a variant of the Koch reaction occurs instead,
and formic acid adds to the alkene to produce a larger
carboxylic acid.[42]
Formic acid anhydride[edit]
An unstable formic anhydride, H(C=O)−O−(C=O)H, can be
obtained by dehydration of formic acid with N,N′-
dicyclohexylcarbodiimide in ether at low temperature.[43]

History[edit]
Some alchemists and naturalists were aware that ant hills
give off an acidic vapor as early as the 15th century. The first
person to describe the isolation of this substance (by the
distillation of large numbers of ants) was the English
naturalist John Ray, in 1671.[44][45] Ants secrete the formic acid
for attack and defense purposes. Formic acid was first
synthesized from hydrocyanic acid by the French
chemist Joseph Gay-Lussac. In 1855, another French
chemist, Marcellin Berthelot, developed a synthesis
from carbon monoxide similar to the process used today.
Formic acid was long considered a chemical compound of
only minor interest in the chemical industry. In the late 1960s,
however, significant quantities became available as a
byproduct of acetic acid production. It now finds increasing
use as a preservative and antibacterial in livestock feed.

Safety[edit]
Formic acid has low toxicity (hence its use as a food
additive), with an LD50 of 1.8 g/kg (tested orally on mice). The
concentrated acid is corrosive to the skin. [6]
Formic acid is readily metabolized and eliminated by the
body. Nonetheless, it has specific toxic effects; the formic
acid and formaldehyde produced as metabolites
of methanol are responsible for the optic nerve damage,
causing blindness, seen in methanol poisoning.[46] Some
chronic effects of formic acid exposure have been
documented. Some experiments on bacterial species have
demonstrated it to be a mutagen.[47] Chronic exposure in
humans may cause kidney damage.[47] Another possible effect
of chronic exposure is development of a skin allergy that
manifests upon re-exposure to the chemical.
Concentrated formic acid slowly decomposes to carbon
monoxide and water, leading to pressure buildup in the
containing vessel. For this reason, 98% formic acid is shipped
in plastic bottles with self-venting caps.
The hazards of solutions of formic acid depend on the
concentration. The following table lists the EU classification of
formic acid solutions: