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Ammonium formate

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Ammonium formate Basic information
Product Name:Ammonium formate
Synonyms:AMMONIUM FORMATE SOLUTION;AMMONIUM FORMIATE;FORMIC ACID, AMMONIUM;FORMIC ACID AMMONIUM SALT;AMMONIUMFORMATE,CRYSTAL,REAGENT;Ammonium formate, 97%, water <3%;Formiate ammonia;AMMONIUM FORMATE extrapure AR
CAS:540-69-2
MF:CH5NO2
MW:63.06
EINECS:208-753-9
Product Categories:Fine Chemicals;AlphabeticalSynthetic Reagents;AmmoniumBiological Buffers;Biological Buffers;BioUltra Buffers;Buffer SolutionsProtein Structural Analysis;Inorganic Salts;Optimization Reagents;X-Ray Crystallography;Industrial/Fine Chemicals;Pyridines
Mol File:540-69-2.mol
Ammonium formate Structure
Ammonium formate Chemical Properties
Melting point 119-121 °C (lit.)
Boiling point 103.28°C (rough estimate)
density 1.26 g/mL at 25 °C (lit.)
vapor pressure 0.033Pa at 25℃
refractive index 1.4164 (estimate)
Fp 104℃
storage temp. Inert atmosphere,Room Temperature
solubility H2O: 10 M at 20 °C, clear, colorless
form Solid
color White
OdorSlight formic acid odour
PH6.53(1 mM solution);6.5(10 mM solution);6.49(100 mM solution);6.45(1000 mM solution)
PH Range6 - 7
Water Solubility soluble
λmaxλ: 260 nm Amax: 0.05
λ: 280 nm Amax: 0.04
Sensitive Hygroscopic
Merck 14,523
BRN 3625095
Stability:Stable. Hygroscopic. Incompatible with strong acids, strong oxidizing agents.
InChI1S/CH2O2.H3N/c2-1-3;/h1H,(H,2,3);1H3
InChIKeyVZTDIZULWFCMLS-UHFFFAOYSA-N
SMILESN.OC=O
LogP-3.34 at 25℃
CAS DataBase Reference540-69-2(CAS DataBase Reference)
EPA Substance Registry SystemAmmonium formate (540-69-2)
Safety Information
Hazard Codes Xi
Risk Statements 36/37/38
Safety Statements 26-36-37/39
WGK Germany 2
RTECS BQ6650000
3-10
TSCA TSCA listed
HS Code 29151200
Storage Class11 - Combustible Solids
Hazard ClassificationsEye Irrit. 2
Hazardous Substances Data540-69-2(Hazardous Substances Data)
ToxicityLD50 orl-mus: 2250 mg/kg ZERNAL 9,332,69
MSDS Information
ProviderLanguage
Ammonium formate English
SigmaAldrich English
ACROS English
ALFA English
Ammonium formate Usage And Synthesis
Chemical PropertiesAmmonium formate, NH4HCO2, is the ammonium salt of formic acid. It is a colorless, hygroscopic, crystalline solid. It can be synthesized through treating ammonium carbonate with 85% formic acid. It is widely used in many organic reactions such as Leuckart reaction which is the reductive amination of aldehydes and ketones. It can also be used as a buffer in HPLC and LC/MS test. Moreover, it is also used in palladium on carbon (Pd/C) reduction of functional group. It can also be used for the preparation of formic acid in situ as well as being used to store formic acid.
Common HPLC Buffers: Ammonium formate (2.7<PH<3.7)
Common HPLC Buffers: Ammonium formate (2.7<PH<3.7) does a fairly good job of filling the gap at the low-pH end.
Physical propertiesWhite monoclinic deliquescent crystals or granules; density 1.280 g/cm3; melts at 116°C; highly soluble in water (102 g/100 g at 0°C), solubility rapidly increasing with temperature (i.e., 531 g/100 g at 80°C); soluble in liquid ammonia, alcohol and ether.
UsesAmmonium formate is widely used in various organic reactions like Leuckart reaction which involves the reductive amination of aldehydes and ketones. It serves as a buffer in high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC/MS). It finds application in palladium on carbon (Pd/C) reduction of functional groups. For example, reduction of alkenes to alkanes and formaldehyde to methanol. It is also used to prepare formic acid insitu as well as used to store formic acid by making it as an ammonium salt.
UsesPure ammonium formate decomposes into formamide and water when heated, and this is its primary use in industry. Formic acid can also be obtained by reacting ammonium formate with a dilute acid, and since ammonium formate is also produced from formic acid, it can serve as a way of storing formic acid.
In chemical analysis, especially to ppt base metals from salts of the "noble" metals. Ammonium formate can also be used in palladium on carbon (Pd / C) reduction of functional groups. In the presence of Pd / C, ammonium formate decomposes to hydrogen, carbon dioxide, and ammonia.
Ammonium formate can be used for reductive amination of aldehydes and ketones (Leuckart reaction)
Ammonium formate can be used as a buffer in high performance liquid chromatography (HPLC), and is suitable for use with liquid chromatography/mass spectrometry (LC/MS). .
Definition ChEBI: Ammonium formate is the ammonium salt of formic acid. It has a role as a buffer. It is functionally related to a formic acid.
ReactionsWhen heated, ammonium formate eliminates water, forming formamide. Upon further heating it forms to HCN and H2O. A side reaction of this is the decomposition of formamide to CO and NH3.
Air & Water ReactionsAmmonium formate is generally soluble in water. 
Reactivity ProfileSalts, basic, such as Ammonium formate, are generally soluble in water. The resulting solutions contain moderate concentrations of hydroxide ions and have pH's greater than 7.0. They react as bases to neutralize acids. These neutralizations generate heat, but less or far less than is generated by neutralization of the bases in reactivity group 10 (Bases) and the neutralization of amines. They usually do not react as either oxidizing agents or reducing agents but such behavior is not impossible.
Health HazardInhalation causes irritation of nose and throat. Ingestion irritates mouth and stomach. Contact with eyes or skin causes irritation.
Fire HazardSpecial Hazards of Combustion Products: Toxic and irritating ammonia and formic acid gases may form in fire.
Safety ProfileModerately toxic by ingestion andintravenous routes. When heated to decomposition itemits toxic fumes of NOx and NH3.
SynthesisAmmonium formate was synthesised by the oxidative degradation of various carbohydrates in the presence of hydrogen peroxide and ammonium hydroxide. The specific reaction conditions are as follows: aldoses/ketoses/disaccharides/trisaccharides (5 mg), 30% H₂O₂ (150 μL), 25% NH₄OH (30 μL), reacted at room temperature for 1 hour. For common aldoses such as glucose, the conversion rate to ammonium formate can reach 99%. With the exception of non-reducing sugars, the majority of carbohydrates studied can be efficiently converted to ammonium formate in aqueous solution under mild and environmentally friendly conditions[1].
Oxidative degradation of carbohydrates to ammonium formate
Purification MethodsHeat the solid in NH3 vapour and dry it in a vacuum till the NH3 odour is faint (note that it can evaporate completely in a vacuum). Recrystallise it from absolute EtOH and then keep it in a desiccator over 99% H2SO4 in vacuo. It is very hygroscopic. It exists in two forms, stable needles and less stable plates. It also forms acid salts, i.e. HCO2NH4.3HCO2H and HCO2NH4.HCO2H. [Kensall & Adler J Am Chem Soc 43 1473 1921, Beilstein 2 IV 18.]
References[1] Prasanna Pullanikat. (2010). Oxidative degradation of reducing carbohydrates to ammonium formate with H2O2 and NH4OH. Tetrahedron Letters, 51 47, Pages 6192-6194. https://doi.org/10.1016/j.tetlet.2010.09.092
References[1] http://www.orgsyn.org/demo.aspx?prep=CV2P0503
[2] https://www.alfa.com/zh-cn/catalog/014517/
[3] https://en.wikipedia.org/wiki/Ammonium_formate
[4] GAO X, MA Y, ZHOU F, et al. Promotion Mechanism of Ammonium Formate in Ammonium Salt Leaching Process for Weathered Crust Elution-Deposited Rare Earth Ores[J]. Minerals, 2023, 1 1: 0. DOI:10.3390/min13101286.
[5] A. S. KORNILOV. Uranium Stripping with Ammonium Acetate and Formate[J]. Radiochemistry, 2024, 65 1 supplement: S172-S176. DOI:10.1134/S1066362223070159.
[6] ISHANI BORTHAKUR, SABUJ KUNDU* Reductive Aminomethylation Using Ammonium Formate and Methanol as N1 and C1 Source: Direct Synthesis of Mono- and Di-Methylated Amines[J]. ACS Catalysis , 2024, 14 8: 5847-5857. DOI:10.1021/acscatal.4c00346.
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