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Potassium formate

Potassium formate, chemically denoted as KHCO₂ or CHKO₂, is the potassium salt of formic acid (HCOOH), appearing as a colorless, hygroscopic crystalline solid with a molecular weight of 84.12 g/mol.^[1]^[2] It exhibits a density of 1.91 g/cm³ and a melting point of 165–168 °C, while being highly soluble in water at approximately 337 g/100 mL at 20 °C.^[2] This compound serves as a versatile buffering agent in chemical formulations due to its ability to maintain pH stability in aqueous solutions.^[1] In the oil and gas industry, potassium formate is a critical additive in high-density, clear brine drilling and completion fluids, particularly for high-pressure, high-temperature (HPHT) wells, where it provides superior well control, lubricity, and inhibition of clay swelling without the need for solid weighting agents like barite.^[3] These formate brines are fully soluble in seawater, recyclable with 80–90% recovery rates, and demonstrate low environmental toxicity, with acute LC50 values ranging from 540 mg/L for Daphnia magna to 6900 mg/L for Mysidopsis bahia.^[3] Beyond drilling, potassium formate functions as an eco-friendly de-icing agent, especially at airports for runway and aircraft treatment, effective in temperatures from -20 °F to 15 °F, with minimal corrosion to metals and rapid biodegradation that poses low risk to groundwater or oxygen levels in water bodies.^[4] It also appears in heat transfer fluids for low-temperature applications and as a reducing agent in select industrial processes, underscoring its broad utility in environmentally conscious operations.^[2]

Properties

Physical properties

Potassium formate has the chemical formula HCOOK and a molecular weight of 84.12 g/mol.^[1] It appears as a white, hygroscopic crystalline powder and is odorless.^[5] The hygroscopic nature causes it to absorb moisture from the air, leading to deliquescence in humid conditions.^[6] The density of the solid is 1.908 g/cm³ at 20°C.^[5] It has a melting point of 167.5°C and decomposes upon further heating without reaching a boiling point.^[1] Potassium formate exhibits high solubility in water, with values increasing markedly with temperature, as shown in the following table:

Temperature (°C)	Solubility (g/100 mL water)
0	32.8
20	331
80	657

It is soluble in methanol, ethanol, and glycerol but insoluble in acetone and benzene.^[8] Aqueous solutions of potassium formate are neutral to slightly alkaline, with a pH around 7-9 for a 10% solution.^[6]

Chemical properties

Potassium formate, as the potassium salt of formic acid, dissociates completely in aqueous solution to yield formate ions (HCOO⁻) and potassium cations (K⁺).^[1] In terms of acid-base properties, potassium formate solutions are weakly basic due to the hydrolysis of the formate ion, the conjugate base of the weak acid formic acid (pKa = 3.75).^[9] It functions effectively as a buffering agent when combined with formic acid, maintaining pH stability in the range around 3.75.^[1] Potassium formate exhibits high thermal stability up to approximately 200°C, beyond which it undergoes decomposition primarily to potassium oxalate and hydrogen gas via the coupling of formate ions.^[10] The compound is generally resistant to oxidation under ambient conditions but can participate in redox reactions where the formate ion serves as a mild reducing agent, capable of reducing certain metal ions such as silver(I) to metallic silver in analytical procedures akin to variants of the Tollens' test.^[11] Potassium formate demonstrates good compatibility with most metals, exhibiting low corrosivity toward ferrous materials and serving as a less aggressive alternative to chloride-based salts in applications requiring material stability.^[12] Additionally, it is readily biodegradable under aerobic conditions, with degradation rates exceeding 70% within 28 days in environmental media such as soil and water.^[13]

Synthesis

Industrial production

Potassium formate is primarily produced on an industrial scale through the neutralization of formic acid with potassium hydroxide or potassium carbonate in aqueous solution. The key reaction is \ce{HCOOH + KOH -> HCOOK + H2O}, which is exothermic and yields potassium formate along with water as the sole by-product. This method is favored for its simplicity, high efficiency, and ability to produce a product with purity exceeding 98%.^[14]^[15]^[16] The reaction is typically carried out under controlled conditions in stirred reactors, with temperatures maintained between 0 and 100°C to facilitate complete neutralization without decomposition or side reactions; excess base is carefully avoided to prevent formation of impurities like potassium oxalate. Following the reaction, the aqueous solution is concentrated via multi-effect evaporation to remove water, after which the product is crystallized, separated by filtration or centrifugation, and dried to obtain solid potassium formate in flake, powder, or granular form. This purification sequence ensures minimal waste and high recovery rates, often above 95%, contributing to the process's economic viability and environmental profile.^[17]^[18] An alternative industrial route, though less commonly employed due to higher energy requirements, involves the reaction of carbon monoxide with potassium hydroxide under elevated pressure (above 690 kPa) and temperature (100–200°C), proceeding as \ce{KOH + CO -> HCOOK}. This high-pressure carbonylation method avoids reliance on formic acid but demands specialized equipment and catalysts in some variants, limiting its adoption compared to the neutralization process.^[16]^[19]^[20] Global production of potassium formate is concentrated in facilities across Europe and Asia, where major chemical manufacturers like BASF operate dedicated plants with capacities reaching tens of thousands of tons annually; output is closely aligned with demand from the oilfield chemicals sector. The overall process generates low waste, primarily water, positioning it as an eco-friendly option in large-scale chemical manufacturing.^[21]^[22]^[23]

Laboratory preparation

Potassium formate is commonly prepared in the laboratory through the neutralization of formic acid with potassium hydroxide. High-purity (p.a. grade) 85% formic acid is slowly added to a standardized aqueous solution of potassium hydroxide while stirring, ensuring complete reaction by monitoring the pH to neutrality or slight basicity (pH 7-8).^[24]^[18] The reaction is typically titrated using phenolphthalein as an indicator, which changes from colorless to pink at the endpoint, allowing precise control for small-scale synthesis.^[25] Following neutralization, the solution is evaporated under reduced pressure to concentrate the product, and the resulting solid is purified by recrystallization from a hot ethanol-water mixture to remove impurities and obtain colorless crystals. The purified salt is then washed with cold ethanol and dried over sulfuric acid in a desiccator.^[24]^[26] This method typically affords yields of 90-95% based on the limiting reagent, with the product's purity confirmed by acid-base titration against a standard or spectroscopic analysis such as IR or NMR to verify the absence of unreacted acid.^[16] The procedure requires the use of a fume hood to mitigate exposure to irritating formic acid vapors and an analytical balance for accurate stoichiometric measurements, ensuring safety and reproducibility on a gram scale suitable for research or educational purposes.^[27] Unlike the less common high-pressure carbonylation method sometimes used industrially, laboratory synthesis prioritizes simplicity and precision without specialized equipment.^[19] An alternative laboratory route involves the direct reaction of potassium bicarbonate with formic acid, yielding potassium formate, water, and carbon dioxide gas via gentle effervescence:

\ce{KHCO3 + HCOOH -> HCOOK + H2O + CO2}

This exothermic process is carried out by adding formic acid dropwise to a suspension of potassium bicarbonate in water at room temperature, followed by evaporation and recrystallization as described above, offering a convenient option when potassium hydroxide is unavailable. Potassium formate was first prepared in laboratories during the 19th century using analogous neutralization techniques, aligning with the early development of organic acid salts following the isolation of formic acid.^[28]

Uses

In petroleum industry

Potassium formate serves as a key component in drilling fluids for the petroleum industry, particularly as a high-density brine used to formulate weighted, solids-free systems in high-pressure/high-temperature (HPHT) wells. Its maximum density of 1.57 g/cm³ at approximately 75-77% concentration enables effective hydrostatic pressure control without the need for solid weighting agents like barite, reducing settling issues and enhancing fluid stability.^[29]^[30]^[31] In water-based muds, potassium formate is typically incorporated at concentrations of 10-50% to achieve desired densities ranging from 8.4 to 13.1 lb/gal, providing low viscosity, high solubility, and compatibility with polymers for improved lubricity and reduced friction compared to traditional cesium or zinc-based brines. It stabilizes shale formations by inhibiting clay hydration and swelling, minimizing borehole instability in water-sensitive reservoirs. These properties make it suitable for non-damaging drill-in and completion fluids, particularly in sensitive shale and sandstone formations.^[32]^[33]^[30] Environmentally, potassium formate offers a biodegradable, non-toxic alternative to chloride-based brines, significantly lowering formation damage, sulfate scaling, and overall ecological impact during offshore operations. Its non-corrosive nature further supports compatibility with drilling equipment, contributing to cost savings in fluid management through reduced waste and simpler disposal.^[34]^[35]^[36] Since the 1990s, potassium formate has been widely adopted in North Sea and Gulf of Mexico operations for HPHT drilling, with case studies demonstrating improved rates of penetration and production optimization in challenging reservoirs. Recent developments as of 2025 include its integration with nanomaterials, such as hydrothermal carbon nanospheres, to enhance thermal stability and performance in ultra-HPHT conditions exceeding 150°C and 10,000 psi.^[37]^[38]^[39]^[40]^[41]

Other applications

Potassium formate serves as an effective de-icing agent in airport runway fluids, typically formulated as 50-75% aqueous solutions that exhibit a low eutectic freezing point around -60°C, enabling efficient ice removal and prevention in harsh winter conditions.^[42]^[43] Its low corrosivity to aircraft materials, combined with compliance to FAA specifications, makes it suitable for aviation applications, while its biodegradability and minimal chemical oxygen demand offer environmental advantages over traditional urea or glycol-based de-icers by reducing runoff pollution and toxicity to aquatic life.^[44]^[45] Potassium formate functions as a buffer in various chemical processes, particularly for pH control in leather tanning where it serves as a neutralizing agent and "camouflage acid" to gradually adjust acidity during chromium tanning, improving penetration and uniformity.^[46] In textile dyeing, it regulates dye bath pH to enhance dye fixation on fibers and prevent uneven coloration.^[47] Additionally, its high ionic conductivity makes it valuable as an electrolyte in alkaline fuel cells, where formate solutions support efficient electron transfer in direct formate fuel cell designs operating up to 80°C.^[48]^[49] As an antifreeze component in heat transfer fluids, potassium formate is employed in solar thermal systems at concentrations of 30-70%, providing non-volatility and thermal stability across a wide range from -60°C to 218°C, which minimizes evaporation losses and supports reliable performance in renewable energy applications.^[50]^[51] Emerging applications as of 2025 include its role in carbon capture and utilization, where electrochemical reduction of CO₂ produces potassium formate as a stable intermediate for CO₂ sequestration and conversion into fuels or chemicals via pilot-scale facilities.^[52] In pharmaceuticals, it functions as a reducing agent and intermediate in syntheses, such as the extraction of coenzyme Q10 or preparation of active compounds.^[53]^[54] While the petroleum industry remains the dominant consumer of potassium formate, non-oilfield applications such as de-icing and heat transfer account for a portion of total global consumption.^[55]

Safety

Toxicity

Potassium formate exhibits low acute toxicity across various exposure routes. The oral LD50 in mice is reported as 5500 mg/kg, exceeding the OECD threshold of 2000 mg/kg for classification as non-toxic. Dermal LD50 values are greater than 2000 mg/kg in rats, based on analogous testing with similar formate salts. Inhalation data for dust forms indicate low hazard potential, with no specific LC50 established but general assessments showing no acute inhalation toxicity classification under GHS criteria.^[56]^[5]^[57] Skin and eye contact with potassium formate results in mild irritation, causing temporary redness and discomfort but no evidence of corrosion, sensitization, or severe damage in rabbit dermal and ocular tests. Ingestion may lead to gastrointestinal upset, including nausea and abdominal pain, particularly at high doses; excessive intake can elevate serum potassium levels, potentially causing hyperkalemia, though such poisoning is rare due to the compound's low inherent toxicity. Human incidents are uncommon.^[56]^[58] Chronic exposure to potassium formate shows no evidence of carcinogenicity, mutagenicity, germ cell mutagenicity, or reproductive toxicity, with regulatory assessments confirming its non-hazardous status under GHS guidelines. Long-term studies are limited, but the absence of target organ toxicity supports safe use in occupational settings at typical exposure levels.^[5]^[59]^[60] Regulatory bodies classify potassium formate as non-hazardous. It is not listed under EPA hazardous substances or SARA Title III sections, and REACH evaluations do not assign it hazard classifications for human health endpoints. Individuals with renal impairment require caution, as impaired potassium excretion may exacerbate risks of hyperkalemia from exposure.^[61]^[62]^[56]

Handling and storage

Potassium formate should be handled with appropriate personal protective equipment (PPE) to minimize exposure risks. For handling the powder form, nitrile rubber gloves (with a breakthrough time of at least 480 minutes), safety goggles or glasses with side shields, and a dust mask or P1 filter respirator are recommended to prevent skin contact, eye irritation, and inhalation of dust. Concentrated solutions require similar PPE, with emphasis on avoiding direct skin contact due to potential mild irritation.^[5]^[63] Storage of potassium formate requires cool, dry, well-ventilated conditions in tightly sealed containers made of plastic or coated steel to protect against its hygroscopic nature. It should be kept away from incompatible materials such as strong acids and oxidizing agents to prevent reactions. Under these conditions, the compound maintains stability for extended periods, typically exceeding two years when shielded from moisture.^[5]^[63]^[64] In the event of a spill, ensure adequate ventilation and avoid generating dust; for powder, sweep up carefully and collect into suitable containers, while for liquids, dike the area and absorb with an inert material such as sand or vermiculite before disposal. Residues may be neutralized with dilute acid if necessary, but ventilation of the area is essential to disperse any fumes.^[5]^[63]^[65] Potassium formate is non-flammable under normal conditions but may decompose during a fire, releasing carbon monoxide, carbon dioxide, hydrogen, and potassium oxides; use water fog, dry chemical, or carbon dioxide for cooling surrounding containers, and firefighters should wear self-contained breathing apparatus.^[5]^[64] For transportation, potassium formate is not classified as a dangerous good and has no UN number, allowing shipment under standard regulations such as ADR, IMDG, and DOT without special precautions.^[5]^[63] Waste disposal involves diluting small quantities with water and flushing to a sewer if permitted by local regulations, as the compound is biodegradable and non-hazardous; larger amounts should be sent to an approved waste disposal facility in sealed containers.^[63]^[56]^[16]

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