Formic acid

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Formic acid
Skeletal structure of formic acid
Skeletal structure of formic acid
3D model of formic acid
3D model of formic acid
Names
Preferred IUPAC name
Formic acid[1]
Systematic IUPAC name
Methanoic acid[1]
Other names
  • Isocarbonous acid
  • Carbonous acid
  • Formylic acid
  • Methylic acid
  • Hydrogencarboxylic acid
  • Hydroxy(oxo)methane
  • Metacarbonoic acid
  • Oxocarbinic acid
  • Oxomethanol
  • Hydroxymethylene oxide
Identifiers
3D model (
JSmol
)
1209246
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard
 100.000.527 Edit this at Wikidata
EC Number
  • 200-579-1
E number E236 (preservatives)
1008
KEGG
RTECS number
  • LQ4900000
UNII
  • InChI=1S/HCOOH/c2-1-3/h1H,(H,2,3) ☒N
    Key: BDAGIHXWWSANSR-UHFFFAOYSA-N checkY
  • InChI=1/HCOOH/c2-1-3/h1H,(H,2,3)
    Key: BDAGIHXWWSANSR-UHFFFAOYAT
  • O=CO
Properties
CH2O2
Molar mass 46.025 g·mol−1
Appearance Colorless fuming liquid
Odor Pungent, penetrating
Density 1.220 g/mL
Melting point 8.4 °C (47.1 °F; 281.5 K)
Boiling point 100.8 °C (213.4 °F; 373.9 K)
Miscible
Solubility Miscible with ether, acetone, ethyl acetate, glycerol, methanol, ethanol
Partially soluble in benzene, toluene, xylenes
log P −0.54
Vapor pressure 35 mmHg (20 °C)[2]
Acidity (pKa) 3.745[3]
Conjugate base
 Formate
−19.90×10−6 cm3/mol
1.3714 (20 °C)
Viscosity 1.57 cP at 268 °C
Structure
Planar
1.41 D (gas)
Thermochemistry
131.8 J/mol K
Std enthalpy of
formation
(ΔfH⦵298)
 −425.0 kJ/mol
Std enthalpy of
combustion
(ΔcH⦵298)
 −254.6 kJ/mol
Pharmacology
QP53AG01 (WHO
)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Corrosive; irritant;
sensitizer
GHS labelling:
GHS02: Flammable GHS05: Corrosive
Danger
H314
P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
2
0
Flash point 69 °C (156 °F; 342 K)
601 °C (1,114 °F; 874 K)
Explosive limits
 14–34%[citation needed]
18–57% (90% solution)[2]
Lethal dose or concentration (LD, LC):
700 mg/kg (mouse, oral), 1100 mg/kg (rat, oral), 4000 mg/kg (dog, oral)[4]
7853 ppm (rat, 15 min)
3246 ppm (mouse, 15 min)[4]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 5 ppm (9 mg/m3)[2]
REL (Recommended)
 TWA 5 ppm (9 mg/m3)[2]
IDLH
(Immediate danger)
 30 ppm[2]
Safety data sheet (SDS) MSDS from JT Baker
Related compounds
Acetic acid
Propionic acid
Related compounds
 Formaldehyde
Methanol
Supplementary data page
Formic acid (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Formic acid (from

anion derived from formic acid are called formates. Industrially, formic acid is produced from methanol.[5]

Natural occurrence

See also:
Insect defenses

In nature, formic acid is found in most

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).[8] Formic acid is a naturally occurring component of the atmosphere primarily due to forest emissions.[9]

History

As early as the 15th century, some

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, significant quantities became available as a byproduct of acetic acid production. It now finds increasing use as a preservative and antibacterial in livestock feed.

Properties

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

Formic acid is a colorless liquid having a pungent, penetrating odor[12] at room temperature, comparable to the related acetic acid. Formic acid is about ten times stronger than acetic acid.

It is

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.[15][16]

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

HCO2H → H2 + CO2

Soluble ruthenium catalysts are also effective.[17][18] Carbon monoxide free hydrogen has been generated in a very wide pressure range (1–600 bar).[17]

Reactant

Formic acid shares most of the chemical properties of other

Fischer esterifications of formic acid, it self-catalyzes the reaction and no additional acid catalyst is needed.[19] Formic acid shares some of the reducing properties of aldehydes, reducing solutions of metal oxides to their respective metal.[20]

Formic acid is a source for a

formyl group for example in the formylation of N-methylaniline to N-methylformanilide in toluene.[21]

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
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.[22]

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.[23]

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 in ether at low temperature.[24]

Production

In 2009, the worldwide capacity for producing formic acid was 720 thousand tonnes (1.6 billion pounds) per year, roughly equally divided between Europe (350 thousand tonnes or 770 million pounds, mainly in Germany) and Asia (370 thousand tonnes or 820 million pounds, mainly in China) while production was below 1 thousand tonnes or 2.2 million pounds per year in all other continents.[25] It is commercially available in solutions of various concentrations between 85 and 99 w/w %.[13] 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 thousand tonnes or 440 million pounds per year, BASF, Germany), Oulu (105 thousand tonnes or 230 million pounds, Eastman, Finland), Nakhon Pathom (n/a, LC Industrial), and Feicheng (100 thousand tonnes or 220 million pounds, Feicheng, China). 2010 prices ranged from around €650/tonne (equivalent to around $800/tonne) in Western Europe to $1250/tonne in the United States.[25]

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:[13]

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

liquid-liquid extraction with an organic base.[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.[13] This oxidative route to acetic acid has declined in importance so that the aforementioned dedicated routes to formic acid have become more important.

Hydrogenation of carbon dioxide

The catalytic hydrogenation of CO2 to formic acid has long been studied. This reaction can be conducted homogeneously.[26][27]

Oxidation of biomass

Formic acid can also be obtained by aqueous catalytic partial oxidation of wet biomass by the OxFA process.[28][29] 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

In the laboratory, formic acid can be obtained by heating oxalic acid in glycerol and extraction by steam distillation.[30] 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.[31]

Pb(HCOO)2 + H2S → 2HCOOH + PbS

Electrochemical production

It has been reported that formate can be formed by the

electrochemical reduction of CO2 (in the form of bicarbonate) at a lead cathode at pH 8.6:[32]

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:

CO2 + OH−
 → HCO−
2 + 1/2 O2

Artificial photosynthesis

In August 2020, researchers at Cambridge University announced a stand-alone advanced 'photosheet' technology that converts sunlight, carbon dioxide and water into oxygen and formic acid with no other inputs.[33]

Biosynthesis

Formic acid is named after ants which have high concentrations of the compound in their venom. In ants, formic acid is derived from

5,10-methenyltetrahydrofolate intermediate.[34] 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.[35]

Uses

Agriculture

A major use of formic acid is as 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.[13] 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.[36] In the poultry industry, it is sometimes added to feed to kill E. coli bacteria.[37][38] Use as a preservative for silage and other animal feed constituted 30% of the global consumption in 2009.[25]

miticide against the tracheal mite (Acarapis woodi) and the Varroa destructor mite and Varroa jacobsoni mite.[39]

Energy

Formic acid can be used in a fuel cell. It can be used directly in formic acid fuel cells or indirectly in hydrogen fuel cells.[40][41]

Electrolytic conversion of electrical energy to chemical fuel has been proposed as a large-scale source of formate by various groups.[42] The formate could be used as feed to modified E. coli bacteria for producing biomass.[43][44] Natural microbes do exist that can feed on formic acid or formate (see Methylotroph).

Formic acid has been considered as a means of hydrogen storage.[45] 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]

It is possible to use formic acid as an intermediary to produce isobutanol from CO2 using microbes.[46][47]

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.

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.[48][49]

Other uses

Formic acid is also significantly used in the production of leather, including

production of rubber[13] consumed 6% of the global production in 2009.[25]

Formic acid is also used in place of mineral acids for various cleaning products,

esters
are artificial flavorings and perfumes.

Formic acid application has been reported to be an effective treatment for warts.[50]

Safety

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.[13]

Formic acid is readily metabolized and eliminated by the body. Nonetheless, it has specific

methanol poisoning.[51] Some chronic effects of formic acid exposure have been documented. Some experiments on bacterial species have demonstrated it to be a mutagen.[52] Chronic exposure in humans may cause kidney damage.[52] 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 Globally Harmonized System of Classification and Labelling of Chemicals for formic acid solutions:[citation needed]

weight percent
) 		Pictogram
H-Phrases
2–10% GHS07: Exclamation mark H315
10–90% GHS05: Corrosive H313
>90% GHS05: Corrosive H314

Formic acid in 85% concentration is flammable, and diluted formic acid is on the U.S. Food and Drug Administration list of food additives.

parts per million
(ppm) of air.

See also

References

  1. ^
    ISBN 978-0-85404-182-4
    .
  2. ^ a b c d e NIOSH Pocket Guide to Chemical Hazards. "#0296". National Institute for Occupational Safety and Health (NIOSH).
  3. ISBN 0-306-43104-1
    .
  4. ^ a b "Formic acid". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health. 4 December 2014. Retrieved 26 March 2015.
  5. ^ "Formic acid". American Chemical Society. Retrieved 21 November 2023.
  6. S2CID 4999650
    .
  7. S2CID 30511107
    .
  8. PMID 22593694
    .
  9. doi:10.1029/91GL01565
    .
  10. doi:10.1098/rstl.1670.0052
    .
  11. ^ Johnson, W. B. (1803). History of the process and present state of animal chemistry.
  12. ^ "OSHA Occupational Chemical Database – Occupational Safety and Health Administration". osha.gov. Archived from the original on 29 April 2021. Retrieved 17 April 2015.
  13. ^
    ISBN 978-3-527-30673-2
    .
  14. ^
    PMID 19344174
    .
  15. ^ Koch, H.; Haaf, W. (1973). "1-Adamantanecarboxylic Acid". Organic Syntheses; Collected Volumes, vol. 5, p. 20.
  16. ^ G. H. Coleman, David Craig (1943). "p-Tolualdehyde". Organic Syntheses; Collected Volumes, vol. 2, p. 583.
  17. ^
    PMID 18393267
    .
  18. ^ G. Laurenczy, C. Fellay, P. J. Dyson, Hydrogen production from formic acid. PCT Int. Appl. (2008), 36pp. CODEN: PIXXD2 WO 2008047312 A1 20080424 AN 2008:502691
  19. ISBN 978-0582462366.{{cite book}}: CS1 maint: multiple names: authors list (link
    )
  20. S2CID 32545113
    .
  21. ^ L. F. Fieser; J. E. Jones (1955). "N-Methylformanilide". Organic Syntheses; Collected Volumes, vol. 3, p. 590.
  22. ISSN 1381-1169
    .
  23. doi:10.1002/cber.19660990410
    .
  24. doi:10.1021/j100021a022
    .
  25. ^ a b c d e f S. N. Bizzari; M. Blagoev (June 2010). "CEH Marketing Research Report: FORMIC ACID". Chemical Economics Handbook. SRI consulting. Archived from the original on 14 September 2011.
  26. ^ P. G. Jessop (2007). J. G. de Vries, C. J. Elsevier (ed.). Handbook of Homogeneous Hydrogenation. Weinheim, Germany: Wiley-VCH. pp. 489–511.
  27. doi:10.1016/j.ccr.2004.05.019
    .
  28. S2CID 97572039
    .
  29. S2CID 93224286
    .
  30. hdl:2027/mdp.39015067135775
    .
  31. ^ Arthur Sutcliffe (1930). Practical Chemistry for Advanced Students (1949 ed.). London: John Murray.
  32. S2CID 98437382
    .
  33. ^ Sampson, Joanna (2 August 2020). "Wireless device makes clean fuel from sunlight, CO2 and water". Gasworld. Retrieved 26 August 2020.
  34. PMID 718985
    .
  35. PMID 1
    .
  36. ^ Organic Acids and Food Preservation, Maria M. Theron, J. F. Rykers Lues
  37. doi:10.1093/japr/14.4.750
    .
  38. doi:10.3382/japr.2006-00116
    .
  39. ^ Hoppe, H.; Ritter, W.; Stephen, E. W. C. (1989). "The control of parasitic bee mites: Varroa jacobsoni, Acarapis woodi and Tropilaelaps clareae with formic acid". American Bee Journal.
  40. doi:10.1016/j.jpowsour.2004.12.031
    .
  41. ^ Jorn Madslien (27 June 2017). "Ant power: Take a ride on a bus that runs on formic acid". BBC News. Retrieved 11 July 2017.
  42. PMID 27459678
    .
  43. PMID 31778652
    .
  44. S2CID 211074951
    .
  45. PMID 18781551
    .
  46. ^ "UCLA Researchers Use Electricity and CO2 to Make Butanol". 30 March 2012.
  47. S2CID 24328552
    .
  48. ^ "Archived copy". Archived from the original on 7 November 2017. Retrieved 7 November 2017.{{cite web}}: CS1 maint: archived copy as title (link)[full citation needed]
  49. PMID 6304128
    .
  50. S2CID 42351889
    .
  51. PMID 11909893
    .
  52. ^ a b "Occupational Safety and Health Guideline for Formic Acid". OSHA. Archived from the original on 20 September 2011. Retrieved 28 May 2011.
  53. ^ 21 CFR 186.1316, 21 CFR 172.515

External links

Wikimedia Commons has media related to Formic acid.
Wikisource has the text of the 1911 Encyclopædia Britannica article "Formic Acid".
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