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Calcium formate
Calcium formate
Calcium formate
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Calcium formate
Calcium formate
Calcium formate
Names
Preferred IUPAC name
Calcium diformate
Other names
  • Formic acid calcium salt
  • calcoform
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.008.058 Edit this at Wikidata
EC Number
  • 208-863-7
E number E238 (preservatives)
KEGG
RTECS number
  • LQ5600000
UNII
  • InChI=1S/2CH2O2.Ca/c2*2-1-3;/h2*1H,(H,2,3);/q;;+2/p-2 checkY
    Key: CBOCVOKPQGJKKJ-UHFFFAOYSA-L checkY
  • 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
Appearance white-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:
GHS05: CorrosiveGHS07: Exclamation mark
Danger
H318
P264, P280, P305+P351+P338, P310, P337+P313
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 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).
☒N verify (what is checkY☒N ?)

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]

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

Uses

[edit]

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 of 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]

In plant cultivation, calcium formate is finding use as a soluble calcium carrier in situations where neither chlorine nor nitrogen are wanted.[6][7]

Research

[edit]

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.[8] 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.[9] 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.[10]

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, which binds sulfur oxides and thus reduces their release to the environment. This process is called wet flue gas desulfurization (WFGS). Calcium formate seems to be more effective than or almost equally as effective as some other industrially used WFGS agents.[11]

Production

[edit]

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.[12] It may also be made from calcium chloride and formic acid.[2]

Safety

[edit]

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.[13]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Calcium formate

View on Grokipedia
from Grokipedia
Calcium formate is the calcium salt of , with the Ca(HCOO)₂ and a molecular weight of 130.11 g/mol. It typically appears as a white to off-white, free-flowing crystalline powder with , a of 2.02 g/cm³, and a of approximately 300 °C. The compound exhibits moderate in (about 160 g/L at 20 °C), forming neutral to slightly alkaline solutions with a ranging from 7.5 to 8.5 depending on concentration. Produced commercially by neutralizing with or , calcium formate serves as a versatile industrial chemical. In the sector, it functions as a non-chloride accelerator for hydration, reducing setting times by up to 30% at dosages of 0.5–2% by weight of and enhancing early , particularly in cold weather applications. It also prevents , improves workability in grouts and self-leveling compounds, and is used in alkali-free formulations. Beyond , calcium formate acts as a feed additive in nutrition, particularly for pigs and , where it promotes growth, supports gut health through acidification, and preserves . In the leather industry, it serves as a masking agent during chrome tanning to improve diffusion and as a substitute for in processes. Additionally, it finds applications as a in products, an antifoaming agent in textiles and production, and a component in and boards for enhanced fire retardancy. While generally low in (oral LD50 in rats: 2650 mg/kg), it can cause serious eye damage upon direct contact, necessitating proper handling precautions.

Chemical identity and properties

Molecular structure

Calcium formate has the chemical formula Ca(HCOO)₂ or equivalently Ca(HCO₂)₂, consisting of one calcium cation (Ca²⁺) and two anions (HCOO⁻ or HCO₂⁻). The is 130.11 g/mol. As an ionic , calcium formate features Ca²⁺ cations and HCOO⁻ anions in a 1:2 stoichiometric ratio, arranged in a crystalline lattice where the calcium ions are coordinated by oxygen atoms from the formate groups. Each Ca²⁺ ion is surrounded by seven oxygen atoms from multiple formate anions, forming distorted pentagonal bipyramidal that links into infinite chains cross-linked by additional calcium ions. The of the α-phase, the stable form at , is orthorhombic with Pbca. The unit cell parameters are a = 10.238(4) Å, b = 6.305(2) Å, c = 13.456(5) Å, and volume V = 868.6(5) ų, containing Z = 8 formula units. Within the anion, the carbon-oxygen bond lengths exhibit partial double-bond character due to , with typical values of C–O ≈ 1.264 Å and C=O ≈ 1.238 Å.

Physical properties

Calcium formate is a white to off-white crystalline powder. It exhibits a faint, slightly acetic acid-like odor. The density of calcium formate is 2.02 g/cm³ at 20 °C. It does not have a distinct melting point but decomposes at approximately 300 °C, yielding calcium carbonate and formaldehyde according to the reaction (HCOO)₂Ca → CaCO₃ + HCHO. Calcium formate is highly soluble in water, with a solubility of about 16 g/100 mL at 20 °C, but it is insoluble in ethanol and diethyl ether. Its ionic nature contributes to this high aqueous solubility. It is non-hygroscopic and demonstrates good flowability, making it suitable for handling in dry conditions.

Production and synthesis

Industrial production

Calcium formate is primarily produced on an industrial scale through the neutralization of with or in . The reaction with proceeds as follows: Ca(OH)2+2HCOOH→Ca(HCOO)2+2H2O\text{Ca(OH)}_2 + 2\text{HCOOH} \rightarrow \text{Ca(HCOO)}_2 + 2\text{H}_2\text{O} This typically occurs at controlled temperatures to manage heat release and ensure complete reaction. Alternatively, serves as a cost-effective calcium source, yielding and as by-products: CaCO3+2HCOOH→Ca(HCOO)2+CO2+H2O\text{CaCO}_3 + 2\text{HCOOH} \rightarrow \text{Ca(HCOO)}_2 + \text{CO}_2 + \text{H}_2\text{O} The reaction is carried out with a molar ratio adjusted for formic acid volatility, often at pH 4-4.5 and moderate stirring (e.g., 60 r/min for 60 minutes). Following the reaction, the solution undergoes crystallization to form uniform granules, facilitated by cooling and concentration. The crude product is then separated via filtration, typically using centrifugal equipment with filter media to achieve moisture content below 5%. Drying follows in a tubular air dryer at 150-180°C, producing a white, crystalline powder. Mother liquor is often recycled to enhance efficiency. Commercial grades achieve purity greater than 98%, with calcium content exceeding 30%. In the , calcium formate emerges as a significant co-product during the synthesis of via of n-butyraldehyde and , using hydrated lime () as the base. Typically, 0.5-1 mol of per mol of n-butyraldehyde neutralizes intermediates, generating calcium alongside the target . This by-product is recovered post-reaction through similar purification steps. Additionally, calcium formate arises as a by-product from the over-reaction of and in certain processes, where excess reactants lead to formate formation beyond intended . This method leverages waste streams for economical recovery, maintaining high purity through standard isolation techniques.

Laboratory preparation

Calcium formate is commonly prepared in laboratory settings through the neutralization of with dilute . The procedure begins by slowly adding finely powdered to a stirred solution of (typically 10-15% concentration) in a reaction vessel, with gentle heating to 50-60°C to promote and complete dissolution via the reaction: CaCO3+2HCOOH→Ca(HCOO)2+H2O+CO2\mathrm{CaCO_3 + 2HCOOH \rightarrow Ca(HCOO)_2 + H_2O + CO_2} The mixture is maintained under stirring for 1-2 hours until no further evolution is observed, indicating completion. Insoluble impurities, if any, are removed by , and the clear filtrate is concentrated by under reduced or gentle heating. occurs upon cooling, yielding white crystals of calcium formate, which can be collected by , washed with cold water, and dried at low temperature. An alternative laboratory method employs the reaction of with , which proceeds exothermically and requires careful addition to control temperature. is gradually added to excess dilute under stirring at , forming the salt directly: CaO+2HCOOH→Ca(HCOO)2+H2O\mathrm{CaO + 2HCOOH \rightarrow Ca(HCOO)_2 + H_2O} The resulting solution is filtered if necessary and evaporated to obtain the product, similar to the neutralization approach. Another variant involves double displacement reactions using calcium salts (e.g., ) and precursors like in aqueous media: CaCl2+2HCOONa→Ca(HCOO)2↓+2NaCl\mathrm{CaCl_2 + 2HCOONa \rightarrow Ca(HCOO)_2 \downarrow + 2NaCl} This metathesis occurs at ambient temperature, with the less soluble calcium formate precipitating out for easy isolation. Laboratory syntheses typically achieve yields of 90-98%, depending on reactant purity and procedural , with the higher end reported when using stoichiometric ratios and pure . For enhanced purity exceeding 99%, the crude product is recrystallized from hot water or , removing residual sodium or ions if present in alternative methods. Analytical techniques such as XRD or FTIR confirm the structure and absence of impurities post-purification. Due to the corrosive and irritating nature of formic acid vapors, all preparations must be conducted in a well-ventilated fume hood, with appropriate personal protective equipment including gloves, goggles, and lab coat. Neutralization reactions release CO₂ gas, necessitating precautions against pressure buildup in closed systems.

Applications

In construction

Calcium formate serves as a key set accelerator in the construction industry, particularly in cement, grout, and mortar formulations. When added at dosages of 0.5-2% by weight of cement, it significantly reduces initial and final setting times by 30-50%, enabling faster project timelines and improved efficiency in cold weather conditions where hydration is slowed. This acceleration enhances early-age performance without compromising the long-term durability of the material, as evidenced by maintained 28-day compressive strengths comparable to unmodified mixes. The mechanism of action involves promoting the early hydration of tricalcium silicate (C₃S), the primary component in responsible for strength development. The formate ions (HCOO⁻) facilitate faster diffusion and of (C-S-H) gel, leading to increased combined content, higher gel/space ratios, and reduced in the hardened paste. This results in notable gains in early , such as up to 31% higher values at early ages with 1% addition, while also improving overall and decreasing permeability to and chemicals. In practical applications, calcium formate is widely incorporated into dry-mix mortars, tile adhesives, and to expedite curing and enhance adhesion properties, often in combination with ethers or blends. Optimal dosages range from 1-3% by cement weight, balancing acceleration with workability.

In animal nutrition

Calcium formate serves as an effective calcium source in , providing approximately 30.5% elemental calcium in a highly bioavailable form. Unlike , which has lower absorption rates in livestock, calcium formate enhances calcium retention and digestibility, supporting skeletal development and overall mineral balance in species such as broilers and pigs. The (EFSA) has approved calcium formate as a technological feed additive and for all animal , with maximum inclusion levels of 12 g/kg complete feed for pigs and 10 g/kg for and other , including ruminants. These levels ensure safety without adverse effects on animal health, consumers, or the environment, while authorizing its use to maintain feed quality. In livestock nutrition, particularly for weanling piglets, calcium formate improves feed efficiency by releasing , which lowers gut and enhances nutrient digestibility, including , crude , and calcium itself. This acidification reduces diarrhea incidence and bacterial load, such as , leading to better growth performance; for instance, supplementation at around 3% has increased daily gain by up to 3.2% and feed conversion efficiency by 3.7% compared to calcium carbonate-based diets. In ruminants, it contributes to mineral supplementation and feed preservation, helping stabilize conditions indirectly through its calcium provision and properties. Beyond calcium delivery, calcium formate enhances overall absorption by optimizing the gastrointestinal environment and acts as a to inhibit bacterial and mold growth in feed, extending shelf life and reducing spoilage risks across , , and diets. Its low profile supports safe inclusion at approved levels, with no significant concerns for cross-species application in animal production.

Other uses

In the leather industry, calcium formate serves as a masking agent during chrome tanning, facilitating more efficient penetration of salts into hides while preventing over-tanning and ensuring uniform quality. When incorporated into tanning formulations at concentrations of 1-5%, it promotes faster diffusion of chrome, resulting in softer and more consistent products. Beyond these applications, calcium formate finds use in various sectors for its chemical versatility. In gypsum boards, it acts as a by decomposing upon heating to release water and , forming and contributing to fire retardancy by endothermic reaction and dilution of combustibles. As a under the designation E238 for in the EU, calcium formate inhibits microbial growth, extending shelf life of feed by acidifying the environment and suppressing mold, , and . In lubricants, it is added to enhance high-temperature stability and reduce wear in machinery applications. Additionally, in , calcium formate serves as a low-cost for converting carboxylic acids to aldehydes, offering an efficient alternative to traditional methods like the . In textiles, calcium formate acts as a pH buffer during dyeing processes, stabilizing acidity to improve dye fixation, penetration, and color uniformity on fabrics.

Safety and toxicology

Human health effects

Calcium formate exhibits low acute oral toxicity, with an LD50 value of 2,650 mg/kg in rats, indicating it is not classified as acutely toxic by this route. Dermal exposure also shows low toxicity, with an LD50 greater than 2,000 mg/kg in rats, and inhalation toxicity is similarly low, with an LC50 greater than 0.67 mg/L over 4 hours in rats. Regarding irritation, calcium formate causes serious eye damage, classified under Category 1 (H318) based on rabbit studies, while it is non-irritant to skin per OECD Test Guideline 404. However, inhalation of dust may cause irritation to the respiratory tract. Chronic exposure to calcium formate shows no evidence of carcinogenicity, as it is not listed by the International Agency for Research on Cancer (IARC), the National Toxicology Program (NTP), or the Occupational Safety and Health Administration (OSHA) as a regulated carcinogen. It is not classified as mutagenic or a germ cell mutagen, based on negative results in standard assays. Similarly, there is no evidence of reproductive toxicity, with no classification under relevant regulatory criteria. As a calcium supplement, calcium formate is considered safe for human use at single daily doses up to 3.9 g, equivalent to 1,200 mg of calcium, without accumulation of formate or adverse effects. In December 2023, the U.S. FDA affirmed its safety as an acidifying agent in animal feed up to specified levels. As of 2025, phase 2 clinical trials are assessing its long-term safety and efficacy for treating hyperhomocysteinemia in humans at doses around 2.6 g/day. For safe handling, protective measures include wearing nitrile gloves, safety goggles, and a P2 filter mask to prevent dust inhalation and contact. In case of eye contact, immediate rinsing with water for at least 15 minutes is recommended, followed by medical attention. Calcium formate is not regulated by OSHA as a .

Environmental impact

Calcium formate is readily biodegradable in environmental systems through microbial formate degradation pathways, where formate ions are metabolized into and , or via photooxidation processes. This rapid breakdown minimizes its persistence in ecosystems. Additionally, its negative log Kow value (approximately -2.1 at 7) signifies low lipophilicity, resulting in negligible potential in aquatic or terrestrial organisms. In aquatic environments, calcium demonstrates low to and other organisms, with acute LC50 values greater than 100 mg/L—such as 2000 mg/L for a 96-hour exposure in standard fish assays based on formate data. Its non-persistent nature in water further reduces ecological risks, as it does not accumulate or form harmful byproducts. assessments also classify it as low hazard, with no observed effect concentrations (NOEC) exceeding 10 mg/L for aquatic . Regarding soil and terrestrial impacts, calcium formate poses minimal adverse effects, acting primarily as a that enhances aggregation, neutralizes acidity, and supports microbial activity without introducing long-term residues. In processes, its use as an additive improves removal efficiency while avoiding persistent , as the compound integrates into natural calcium cycles. Overall, it contributes positively to in agricultural applications. From a regulatory perspective, calcium formate is deemed low risk for environmental release; the EPA established an exemption from tolerance requirements for its residues in agricultural commodities in , reflecting its safety profile. Similarly, it is evaluated as environmentally safe in scenarios, with straightforward degradation aligning with protection standards. The has also confirmed its lack of significant ecological concerns in feed additive uses.

Research and developments

Nutritional studies

Nutritional studies on have primarily focused on its role as a calcium source in dietary supplementation, evaluating both and in and animals. In trials, calcium formate has demonstrated high and when administered orally. A pharmacokinetic study of a single 3.9 g oral dose of calcium formate in subjects showed rapid absorption with a peak plasma formate level of 0.50 mmol/L and rapid elimination ( 59 minutes), suggesting no accumulation with repeated dosing such as 1.3 g three times daily. Another confirmed systemic and ocular in healthy volunteers at similar doses, with no changes in serum calcium, ionized calcium, or other biochemical markers, supporting its potential use in preventing calcium deficiency-related conditions such as . In animal nutrition, particularly for species like piglets, (EFSA) assessments from 2014 to 2020 have affirmed the safety of calcium formate as a feed at levels up to 15,000 mg/kg for pigs, with no observed adverse effects on target animals, consumers, users, or the environment. These evaluations noted no detectable residues in or that would pose consumer risks. Recent investigations between 2020 and 2025 have emphasized calcium formate's superior compared to traditional calcium salts like and citrate, particularly in animals. A 2005 bioavailability study, referenced in ongoing market and nutritional reviews, demonstrated that calcium formate delivers calcium to the bloodstream more efficiently, with serum calcium increases 2-3 times higher than equivalents from or citrate in models, a trend extrapolated to monogastrics due to similar digestive . This enhanced absorption, driven by formate's and lack of interference with gastric , supports its application in improving calcium status without the gastrointestinal issues associated with less soluble forms. Despite these findings, nutritional research on calcium formate remains limited by the scarcity of long-term chronic studies in humans, with most derived from short-term pharmacokinetic and acute safety trials rather than extended efficacy outcomes for conditions like . Animal studies, while robust for performance metrics, predominantly focus on short-term growth benefits in production settings, leaving gaps in lifelong impacts.

Material science applications

Recent has explored the role of calcium in enhancing the performance of cementless composites, particularly in CaO-activated strain-hardening formulations. A 2025 study demonstrated that incorporating 1-2% calcium as an accelerator in CaO-activated (GGBFS) composites significantly improves microstructure density by promoting denser hydration products and reducing . This addition leads to substantial gains in mechanical properties, including a 40% increase in compared to unmodified composites, making it promising for durable, low-carbon construction materials. In , calcium formate has been used as a for converting carboxylic acids to aldehydes, providing equivalents under mild conditions. Sustainable applications of calcium formate include eco-friendly synthesis routes via CO₂ mineralization and utilization in green drilling fluids. Between 2023 and 2025, several studies have advanced processes for producing calcium formate directly from CO₂ using heterogenized catalysts, enabling selective conversion with reduced energy input and carbon capture integration; for instance, one method achieves a 24% cost reduction and 57% lower compared to conventional routes. Additionally, its incorporation into drilling fluids enhances stability under high-pressure conditions while minimizing environmental impact. As of 2025, the global calcium formate market size is estimated at approximately $746 million. on high-purity calcium formate (≥99%) produced from waste-derived processes, such as paper sludge, has been reported.

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  62. https://www.bointe.com/a-simple-guide-to-calcium-formate-uses-across-multiple-industries/
  63. https://www.researchnester.com/reports/calcium-formate-market/4536
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