Calcium formate

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Calcium formate
Calcium formate structure.png
Calcium diformate ball-and-stick.png
Names
Preferred IUPAC name
Calcium diformate
Other names
  • Formic acid calcium salt
  • calcoform
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.008.058 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 208-863-7
E number E238 (preservatives)
KEGG
PubChem CID
RTECS number
  • LQ5600000
UNII
  • InChI=1S/2CH2O2.Ca/c2*2-1-3;/h2*1H,(H,2,3);/q;;+2/p-2 X mark.svgN
    Key: CBOCVOKPQGJKKJ-UHFFFAOYSA-L Yes check.svgY
  • InChI=1/2CH2O2.Ca/c2*2-1-3;/h2*1H,(H,2,3);/q;;+2/p-2
    Key: CBOCVOKPQGJKKJ-NUQVWONBAS
  • [Ca+2].[O-]C=O.[O-]C=O
Properties
Ca(HCO2)2
Molar mass 130.113 g/mol
Appearancewhite-to-yellow crystals or crystalline powder [1]
Odor smells slightly like acetic acid [2]
Density 2.02 g/cm3 [3]
Melting point decomposes at 300 °C [3]
16.1 g/100 g (0 °C)
18.4 g/100 g (100 °C)
Solubility insoluble in ethanol [3]
methanol:
0.27 g/100 g (15 °C)
0.23 g/100 g (66 °C) [4]
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H318
P264, P280, P305+P351+P338, P310, P337+P313
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
0
0
Lethal dose or concentration (LD, LC):
rats: 2640 mg/kg (oral), 154 mg/kg (IV) [4]
Related compounds
Other anions
Calcium acetate
Other cations
Sodium formate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Calcium formate is the calcium salt of formic acid. It is also known as E238. Under this E number it is used as an animal feed preservative within EU, but not in foods intended for people. [5]

Contents

Calcium formate is stable at room temperature, [5] is inflammable and forms orthorhombic crystals. [2] The mineral form is very rare and called formicaite, and is known from a few boron deposits.

Uses

Calcium formate is used within EU as an animal feed preservative. It acidifies the feed thus preventing microbe growth and increasing shelf life. About 15 g of calcium formate addition per kg of feed lowers its pH by one. 15 g/kg is the maximum recommended feed concentration within EU – this level is thought to be safe for pigs, chickens, fish and ruminants. The compound is not environmentally harmful in feed use at these levels. Calcium formate prevents the growth bacteria such as E. coli, Pseudomonas aeruginosa, Staphylococcus aureus and Enterococcus hirae in growth mediums. It also prevents the growth of fungi like Aspergillus niger and Candida albicans . However, the relevance of these experimental observations to feed preservation is not known. [5]

Calcium formate is used as a masking agent in the chrome tanning of leather. Calcium formate in tannage formulation promotes faster, more efficient leather penetration of the chrome. Calcium formate can also be used as a replacement for formic acid in the pickling operation. [4]

As a grout and cement additive, calcium formate imparts a number of desirable properties in the final product, e.g. increased hardness and decreased setting time. Its addition is desirable for work at low temperature and for inhibition of corrosion of metal substrates within cement/grout. It is also effective in the prevention of efflorescence. In drywall (gypsum board), calcium formate can function as a fire retardant. [4]

Calcium formate and urea mixtures are effective deicers, and tend to cause less corrosion of steel and cement surfaces relative to some other deicers. [4]

Research

Calcium formate seems to be safe as a calcium supplement for people with one time doses of 3.9 g (1200 of calcium) per day. [6] Increases in blood formate concentration have been observed with such doses, but in healthy subjects the formate does not accumulate, and is quickly metabolized. Calcium formate is shown to be more readily absorbed form of calcium than calcium carbonate and calcium citrate. [7] No optic nerve damage has been observed with calcium formate supplementation – along with formaldehyde, formate is a major metabolic product of methanol, which can cause blindness upon ingestion. [8]

Calcium formate could be used to remove environmentally harmful (see acid rain) sulfur oxides (SOX) from fossil fuel exhausts of e.g. power plants. Calcium formate is added to wet calcium carbonate to promote the formation of gypsum when exhaust is run through it. This process is called wet flue gas desulfurization (WFGS). Gypsum binds sulfur oxides thus reducing their release to the environment via exhaust. Calcium formate seems to be more effective than or almost equally as effective as some other industrially used WFGS agents. [9]

Production

Calcium formate is formed as a co-product during trimethylolpropane production. Hydrated lime (calcium hydroxide) is used as the source of calcium. Butyraldehyde and formaldehyde react in a water solution in the presence of a basic catalyst, forming an unstable intermediate product, dimethylol butyraldehyde (DIMBA). DIMBA reacts further with formaldehyde to give trimethylolpropane and calcium formate. Calcium formate is separated from the solution, heat treated to remove formaldehyde and then dried. [5]

Calcium formate can also be made from calcium hydroxide and carbon monoxide at high pressure and temperature [2] – e.g., at 180 °C and 35 atm. [10] It may also be made from calcium chloride and formic acid. [2]

Safety

Pure calcium formate powder irritates eyes severely, but causes no skin irritation. Powder inhalation can be dangerous. [5] The compound has a stinging taste. Ingesting liquids with high calcium formate concentrations cause severe gastrointestinal lesions. [11]

Related Research Articles

<span class="mw-page-title-main">Gypsum</span> Soft calcium sulfate mineral

Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula CaSO4·2H2O. It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, drywall and blackboard or sidewalk chalk. Gypsum also crystallizes as translucent crystals of selenite. It forms as an evaporite mineral and as a hydration product of anhydrite. The Mohs scale of mineral hardness defines gypsum as hardness value 2 based on scratch hardness comparison.

<span class="mw-page-title-main">Potassium ferrocyanide</span> Chemical compound

Potassium ferrocyanide is the inorganic compound with formula K4[Fe(CN)6]·3H2O. It is the potassium salt of the coordination complex [Fe(CN)6]4−. This salt forms lemon-yellow monoclinic crystals.

<span class="mw-page-title-main">Calcium carbonate</span> Chemical compound

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It is a common substance found in rocks as the minerals calcite and aragonite, most notably in chalk and limestone, eggshells, gastropod shells, shellfish skeletons and pearls. Materials containing much calcium carbonate or resembling it are described as calcareous. Calcium carbonate is the active ingredient in agricultural lime and is produced when calcium ions in hard water react with carbonate ions to form limescale. It has medical use as a calcium supplement or as an antacid, but excessive consumption can be hazardous and cause hypercalcemia and digestive issues.

<span class="mw-page-title-main">Pantothenic acid</span> Chemical compound

Pantothenic acid (vitamin B5) is a B vitamin and an essential nutrient. All animals need pantothenic acid in order to synthesize coenzyme A (CoA), which is essential for cellular energy production and for the synthesis and degradation of proteins, carbohydrates, and fats.

<span class="mw-page-title-main">Formic acid</span> Simplest carboxylic acid (HCOOH)

Formic acid, systematically named methanoic acid, is the simplest carboxylic acid, and has the chemical formula HCOOH and structure H−C(=O)−O−H. It 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.

<span class="mw-page-title-main">Calcium sulfate</span> Laboratory and industrial chemical

Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris, and another occurs naturally as the mineral gypsum. It has many uses in industry. All forms are white solids that are poorly soluble in water. Calcium sulfate causes permanent hardness in water.

<span class="mw-page-title-main">Trisodium citrate</span> Chemical compound

Trisodium citrate has the chemical formula of Na3C6H5O7. It is sometimes referred to simply as "sodium citrate", though sodium citrate can refer to any of the three sodium salts of citric acid. It possesses a saline, mildly tart flavor, and is a mild alkali.

<span class="mw-page-title-main">Calcium citrate</span> Chemical compound

Calcium citrate is the calcium salt of citric acid. It is commonly used as a food additive (E333), usually as a preservative, but sometimes for flavor. In this sense, it is similar to sodium citrate. Calcium citrate is also found in some dietary calcium supplements. Calcium makes up 24.1% of calcium citrate (anhydrous) and 21.1% of calcium citrate (tetrahydrate) by mass. The tetrahydrate occurs in nature as the mineral Earlandite.

<span class="mw-page-title-main">Deicing</span> Process of removing ice, snow, or frost from a surface

Deicing is the process of removing snow, ice or frost from a surface. Anti-icing is the application of chemicals that not only deice but also remain on a surface and continue to delay the reformation of ice for a certain period of time, or prevent adhesion of ice to make mechanical removal easier.

<span class="mw-page-title-main">Lime (material)</span> Calcium oxides and/or hydroxides

Lime is an inorganic material composed primarily of calcium oxides and hydroxides, usually calcium oxide and/or calcium hydroxide. It is also the name for calcium oxide which occurs as a product of coal-seam fires and in altered limestone xenoliths in volcanic ejecta. The International Mineralogical Association recognizes lime as a mineral with the chemical formula of CaO. The word lime originates with its earliest use as building mortar and has the sense of sticking or adhering.

<span class="mw-page-title-main">Potassium citrate</span> Chemical compound

Potassium citrate (also known as tripotassium citrate) is a potassium salt of citric acid with the molecular formula K3C6H5O7. It is a white, hygroscopic crystalline powder. It is odorless with a saline taste. It contains 38.28% potassium by mass. In the monohydrate form, it is highly hygroscopic and deliquescent.

<span class="mw-page-title-main">Potassium acetate</span> Colourless soluble salt of acetic acid

Potassium acetate (also called potassium ethanoate), (CH3COOK) is the potassium salt of acetic acid. It is a hygroscopic solid at room temperature.

<span class="mw-page-title-main">Sodium formate</span> Chemical compound

Sodium formate, HCOONa, is the sodium salt of formic acid, HCOOH. It usually appears as a white deliquescent powder.

<span class="mw-page-title-main">Cement clinker</span> Main component of Portland cement

Cement clinker is a solid material produced in the manufacture of portland cement as an intermediary product. Clinker occurs as lumps or nodules, usually 3 millimetres (0.12 in) to 25 millimetres (0.98 in) in diameter. It is produced by sintering limestone and aluminosilicate materials such as clay during the cement kiln stage.

<span class="mw-page-title-main">Magnesium citrate</span> Chemical compound

Magnesium citrate is a magnesium preparation in salt form with citric acid in a 1:1 ratio. It contains 11.23% magnesium by weight.

<span class="mw-page-title-main">Cement mill</span>

A cement mill is the equipment used to grind the hard, nodular clinker from the cement kiln into the fine grey powder that is cement. Most cement is currently ground in ball mills and also vertical roller mills which are more effective than ball mills.

<span class="mw-page-title-main">Calcium sulfite</span> Chemical compound

Calcium sulfite, or calcium sulphite, is a chemical compound, the calcium salt of sulfite with the formula CaSO3·x(H2O). Two crystalline forms are known, the hemihydrate and the tetrahydrate, respectively CaSO3·½(H2O) and CaSO3·4(H2O). All forms are white solids. It is most notable as the product of flue-gas desulfurization.

<span class="mw-page-title-main">Calcium bisulfite</span> Chemical compound

Calcium bisulfite is an inorganic compound which is the salt of a calcium cation and a bisulfite anion. It may be prepared by treating lime with an excess of sulfur dioxide and water. As a food additive it is used as a preservative under the E number E227. Calcium bisulfite is an acid salt and behaves like an acid in aqueous solution. It is used in the sulfite process for producing paper from wood chips.

<span class="mw-page-title-main">Concrete degradation</span> Damage to concrete affecting its mechanical strength and its durability

Concrete degradation may have many different causes. Concrete is mostly damaged by the corrosion of reinforcement bars due to the carbonatation of hardened cement paste or chloride attack under wet conditions. Chemical damages are caused by the formation of expansive products produced by various chemical reactions, by aggressive chemical species present in groundwater and seawater, or by microorganisms. Other damaging processes can also involve calcium leaching by water infiltration and different physical phenomena initiating cracks formation and propagation. All these detrimental processes and damaging agents adversely affects the concrete mechanical strength and its durability.

<span class="mw-page-title-main">Amorphous calcium carbonate</span>

Amorphous calcium carbonate (ACC) is the amorphous and least stable polymorph of calcium carbonate. ACC is extremely unstable under normal conditions and is found naturally in taxa as wide-ranging as sea urchins, corals, mollusks, and foraminifera. It is usually found as a monohydrate, holding the chemical formula CaCO3·H2O; however, it can also exist in a dehydrated state, CaCO3. ACC has been known to science for over 100 years when a non-diffraction pattern of calcium carbonate was discovered by Sturcke Herman, exhibiting its poorly-ordered nature.

References

  1. "ICSC 1634 – Calcium formate". www.ilo.org. Retrieved 2019-02-12.
  2. 1 2 3 4 The Merck index. S Budavari, M O'Neil, A Smith (12th ed.). Chapman & Hall Electronic Pub. Division. 2000. p. 1675. ISBN   9781584881292.{{cite book}}: CS1 maint: others (link)
  3. 1 2 3 Haynes, William M. (2014). "4". CRC handbook of chemistry and physics. Haynes, WM (95th ed.). p. 55. ISBN   9781482208689.
  4. 1 2 3 4 5 "Calcium Formate Product Data" (PDF). GEO Specialty Chemicals. 2015. Retrieved 2019-02-11.
  5. 1 2 3 4 5 "Scientific Opinion on the safety and efficacy of calcium formate when used as a technological additive for all animal species". EFSA Journal. 12 (11). 2014. doi: 10.2903/j.efsa.2014.3898 . ISSN   1831-4732.
  6. Hanzlik, RP; Fowler, SC; Eells, JT (2005). "Absorption and elimination of formate following oral administration of calcium formate in female human subjects". Drug Metabolism and Disposition. 33 (2): 282–286. doi:10.1124/dmd.104.001289. hdl: 1808/5937 . ISSN   0090-9556. PMID   15547050. S2CID   5956107.
  7. Hanzlik, RP; Fowler, SC; Fisher, DH (2005). "Relative bioavailability of calcium from calcium formate, calcium citrate, and calcium carbonate". The Journal of Pharmacology and Experimental Therapeutics. 313 (3): 1217–1222. doi:10.1124/jpet.104.081893. hdl: 1808/5936 . ISSN   0022-3565. PMID   15734899. S2CID   4976426.
  8. MM Altaweel; et al. (2009). "Ocular and systemic safety evaluation of calcium formate as a dietary supplement" (PDF). Journal of Ocular Pharmacology and Therapeutics. 25 (3): 223–230. doi:10.1089/jop.2008.0128. hdl: 1808/8319 . ISSN   1557-7732. PMID   19456257.
  9. Z Li; et al. (2017). "Effect of calcium formate as an additive on desulfurization in power plants". Journal of Environmental Sciences. 67: 89–95. doi:10.1016/j.jes.2017.06.023. PMID   29778177.
  10. USpatent 1920851A,"Process for producing formates of alkaline earth metals"
  11. Scott, DJ; van Wijk, N (2000). "Comparison in dairy cattle of mucosal toxicity of calcium formate and calcium chloride in oil". New Zealand Veterinary Journal. 48 (1): 24–26. doi:10.1080/00480169.2000.36153. ISSN   0048-0169. PMID   16032113. S2CID   42365225.