Formic acid

Formic acid (Template:Ety), systematically named methanoic acid, is the simplest carboxylic acid. It has the chemical formula HCOOH and structure Template:Chem2. This acid is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. Esters, salts, and the anion derived from formic acid are called formates. Industrially, formic acid is produced from methanol.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

Natural occurrence

Formic acid, which has a pungent, penetrating odor, is found naturally in insects, weeds, fruits and vegetables, and forest emissions. It appears in most ants and in stingless bees of the genus Oxytrigona.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> Wood ants from the genus Formica can spray formic acid on their prey or to defend the nest. The puss moth caterpillar (Cerura vinula) will spray it as well when threatened by predators. It is also found in the trichomes of stinging nettle (Urtica dioica). Apart from that, this acid is incorporated in many fruits such as pineapple (0.21 mg per 100 g), apple (2 mg per 100 g) and kiwi (1 mg per 100 g), as well as in many vegetables, namely onion (45 mg per 100 g), eggplant (1.34 mg per 100 g) and, in extremely low concentrations, cucumber (0.11 mg per 100 g).<ref>Template:Cite journal</ref> Formic acid is a naturally occurring component of the atmosphere primarily due to forest emissions.<ref>Template:Cite journal</ref>

History

As early as the 15th century, some alchemists and naturalists were aware that ant hills give off an acidic vapor. 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.<ref>Template:Cite journal</ref><ref>Template:Cite book</ref> 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.<ref name="Monarch">{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

Formic acid was long considered a chemical compound of only minor interest in the chemical industry. In the late 1960s, significant quantities became available as a byproduct of acetic acid production. It now finds increasing use as a preservative and antibacterial in livestock feed.<ref name="Monarch"/>

Properties

File:Formic Acid Hydrogenbridge V.1.svg

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

Formic acid is a colorless liquid having a pungent, penetrating odor<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> at room temperature, comparable to the related acetic acid. Formic acid is about ten times stronger than acetic acid having a (logarithmic) dissociation constant of 3.745 compared to 4.756 for acetic acid.<ref name="Smith R"/>

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.<ref name=Ullmann_2009>Template:Cite book</ref><ref name=Balabin_2009>Template:Cite journal</ref> Owing to its tendency to hydrogen-bond, gaseous formic acid does not obey the ideal gas law.<ref name=Balabin_2009/> 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 high-boiling azeotrope with water (107.3 °C; 77.5% formic acid). Liquid formic acid tends to supercool.

Chemical reactions

Decomposition

Formic acid readily decomposes by dehydration in the presence of concentrated sulfuric acid to form carbon monoxide and water:

HCO₂H → H₂O + CO

Treatment of formic acid with sulfuric acid is a convenient laboratory source of CO.<ref name="koch">Template:Cite journal</ref><ref name="coleman">Template:OrgSynth</ref>

In the presence of platinum, it decomposes with a release of hydrogen and carbon dioxide.

HCO₂H → H₂ + CO₂

Soluble ruthenium catalysts are also effective for producing carbon monoxide-free hydrogen.<ref name="Fellay2008">Template:Cite journal</ref>

Reactant

Formic acid shares most of the chemical properties of other carboxylic acids. Because of its high acidity, solutions in alcohols form esters spontaneously; in Fischer esterifications of formic acid, it self-catalyzes the reaction and no additional acid catalyst is needed.<ref>Template:Cite book</ref> Formic acid shares some of the reducing properties of aldehydes, reducing solutions of metal oxides to their respective metal.<ref>Template:Cite book</ref>

Formic acid is a source for a formyl group for example in the formylation of N-methylaniline to N-methylformanilide in toluene.<ref>Template:OrgSynth</ref>

In synthetic organic chemistry, formic acid is often used as a source of hydride ion, as in the Eschweiler–Clarke reaction:

The Eschweiler–Clark reaction

It is used as a source of hydrogen in transfer hydrogenation, as in the Leuckart reaction to make amines, and (in aqueous solution or in its azeotrope with triethylamine) for hydrogenation of ketones.<ref name="Zhou2012">Template:Cite journal</ref>

Addition to alkenes

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.<ref>Template:Cite journal</ref>

Formic acid anhydride

An unstable formic anhydride, H(C=O)−O−(C=O)H, can be obtained by dehydration of formic acid with [[N,N'-Dicyclohexylcarbodiimide|N,Template:Prime-dicyclohexylcarbodiimide]] in ether at low temperature.<ref name=gwu>Template:Cite journal</ref>

Production

In 2009, the worldwide capacity for producing formic acid was Template:Convert per year, roughly equally divided between Europe (Template:Convert, mainly in Germany) and Asia (Template:Convert, mainly in China) while production was below Template:Convert per year in all other continents.<ref name=CEH>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> It is commercially available in solutions of various concentrations between 85 and 99 w/w %.<ref name = Ullmann_2009/> Template:As of, the largest producers are BASF, Eastman Chemical Company, LC Industrial, and Feicheng Acid Chemicals, with the largest production facilities in Ludwigshafen (Template:Convert per year, BASF, Germany), Oulu (Template:Convert, Eastman, Finland), Nakhon Pathom (n/a, LC Industrial), and Feicheng (Template:Convert, Feicheng, China). 2010 prices ranged from around €650/tonne (equivalent to around $800/tonne) in Western Europe to $1250/tonne in the United States.<ref name=CEH/>

Regenerating CO₂ to make useful products, that displace incumbent fossil fuel based pathways is a more impactful process than CO₂ sequestration.

Both formic acid and CO (carbon monoxide) are C1 (one carbon molecules).  Formic is a hydrogen-rich liquid which can be transported and easily donates its hydrogen to enable a variety of condensation and esterification reactions to make a wide variety of derivative molecules.  CO, while more difficult to transport as a gas, is also one of the primary constituents of syngas useful in synthesizing a wide variety of molecules.  

CO₂ electrolysis is distinct from photosynthesis and offers a promising alternative to accelerate decarbonization. By converting CO₂ into products using clean electricity, we reduce CO₂ emissions in two ways: first and most simply by the amount of CO₂ that is regenerated, but the second way is less obvious but even more consequential by avoiding the CO₂ emissions otherwise generated by making these same products from fossil fuels. This is known as carbon displacement or abatement.

CO₂ electrolysis holds promise for reducing atmospheric CO₂ levels and providing a sustainable method for producing chemicals, materials, and fuels. Its efficiency and scalability are active areas of research, but now also commercialization, aiming to make it a viable commercial technology for both carbon management and molecule production.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

From methyl formate and formamide

When methanol and carbon monoxide are combined in the presence of a strong base, the result is methyl formate, according to the chemical equation:<ref name=Ullmann_2009/>

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.Template:Citation needed

Niche and obsolete chemical routes

By-product of acetic acid production

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.<ref name=Ullmann_2009/> This oxidative route to acetic acid has declined in importance so that the aforementioned dedicated routes to formic acid have become more important.Template:Cn

Hydrogenation of carbon dioxide

The catalytic hydrogenation of CO₂ to formic acid has long been studied. This reaction can be conducted homogeneously.<ref>Template:Cite book</ref><ref>Template:Cite journal</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

Oxidation of biomass

Formic acid can also be obtained by aqueous catalytic partial oxidation of wet biomass by the OxFA process.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> 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.Template:Citation needed

Laboratory methods

In the laboratory, formic acid can be obtained by heating oxalic acid in glycerol followed by steam distillation.<ref name="chattaway">Template:Cite journal</ref> 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 → HCO₂H + CO₂

Another illustrative method involves the reaction between lead formate and hydrogen sulfide, driven by the formation of lead sulfide.<ref>Template:Cite book</ref>

Pb(HCOO)₂ + H₂S → 2HCOOH + PbS

Electrochemical production

Formate is formed by the electrochemical reduction of CO₂ (in the form of bicarbonate) at a lead cathode at pH 8.6:<ref>Template:Cite journal</ref>

Template:Chem + Template:Chem + 2e⁻ → Template:Chem + 2Template:Chem

or

Template:Chem + Template:Chem + 2e⁻ → Template:Chem + Template:Chem

If the feed is Template:Chem and oxygen is evolved at the anode, the total reaction is:

Template:CO2 + Template:Chem → Template:Chem + 1/2 Template:O2

Biosynthesis

Formic acid is named after ants which have high concentrations of the compound in their venom, derived from serine through a 5,10-methenyltetrahydrofolate intermediate.<ref>Template:Cite journal</ref> 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.<ref>Template:Cite journal</ref>

Uses

Agriculture

A major use of formic acid is as a preservative and antibacterial agent in livestock feed. It arrests certain decay processes and causes the feed to retain its nutritive value longer,

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.<ref name = Ullmann_2009/> It is widely used to preserve winter feed for cattle,<ref>Organic Acids and Food Preservation, Maria M. Theron, J. F. Rykers Lues</ref> and is sometimes added to poultry feed to kill E. coli bacteria.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> Use as a preservative for silage and other animal feed constituted 30% of the global consumption in 2009.<ref name=CEH/>

Beekeepers use formic acid as a miticide against the tracheal mite (Acarapis woodi) and the Varroa destructor mite and Varroa jacobsoni mite.<ref>Template:Cite journal</ref>

Energy

Formic acid can be used directly in formic acid fuel cells or indirectly in hydrogen fuel cells.<ref>Template:Cite journal</ref><ref>Template:Cite news</ref>

Electrolytic conversion of electrical energy to chemical fuel has been proposed as a large-scale source of formate by various groups.<ref>Template:Cite journal</ref> The formate could be used as feed to modified E. coli bacteria for producing biomass.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> Natural methylotroph microbes can feed on formic acid or formate.

Formic acid has been considered as a means of hydrogen storage.<ref>Template:Cite journal</ref> 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).Template:Citation needed

It is possible to use formic acid as an intermediary to produce isobutanol from Template:CO2 using microbes.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>Template:Cite journal</ref>

Soldering

Formic acid has a potential application in soldering. Due to its capacity to reduce oxide layers, formic acid gas can be blasted at an oxide surface to increase solder wettability.Template:Cn

Chromatography

Formic acid is used as a volatile pH modifier in HPLC and capillary electrophoresis. 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.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}Template:Full citation needed</ref><ref>Template:Cite journal</ref>

Other uses

Formic acid is also significantly used in the production of leather, including tanning (23% of the global consumption in 2009<ref name=CEH/>), and in dyeing and finishing textiles (9% of the global consumption in 2009<ref name=CEH/>) because of its acidic nature. Use as a coagulant in the production of rubber<ref name = Ullmann_2009/> consumed 6% of the global production in 2009.<ref name=CEH/>

Formic acid is also used in place of mineral acids for various cleaning products,<ref name =Ullmann_2009/> such as limescale remover and toilet bowl cleaner. Some formate esters are artificial flavorings and perfumes.

Formic acid application has been reported to be an effective treatment for warts.<ref name="pmid11589750">Template:Cite journal</ref>

Safety

Formic acid has low toxicity (hence its use as a food additive), with an Template:LD50 of 1.8Template:Nbspg/kg (tested orally on mice). The concentrated acid is corrosive to the skin.<ref name=Ullmann_2009/>

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.<ref>Template:Cite journal</ref> Some chronic effects of formic acid exposure have been documented. Some experiments on bacterial species have demonstrated it to be a mutagen.<ref name="osha.gov">{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> Chronic exposure in humans may cause kidney damage.<ref name="osha.gov"/> 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.Template:Cn

The hazards of solutions of formic acid depend on the concentration. The following table lists the Globally Harmonized System of Classification and Labelling of Chemicals for formic acid solutions:Template:Citation needed

Concentration (weight percent)	Pictogram	H-Phrases
2–10%	Template:GHS07	Template:H-phrases
10–90%	Template:GHS05	Template:H-phrases
>90%	Template:GHS05	Template:H-phrases

Formic acid in 85% concentration is flammable, and diluted formic acid is on the U.S. Food and Drug Administration list of food additives.<ref>Template:CodeFedReg, Template:CodeFedReg</ref> The principal danger from formic acid is from skin or eye contact with the concentrated liquid or vapors. The U.S. OSHA Permissible Exposure Level (PEL) of formic acid vapor in the work environment is 5 parts per million (ppm) of air.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>

See also

• Orthoformic acid
• Formic acid vehicle

External links

• International Chemical Safety Card 0485.
• NIOSH Pocket Guide to Chemical Hazards.
• ChemSub Online (Formic acid).