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)

Flash point:

104℃

storage temp. 

Inert atmosphere,Room Temperature

solubility 

H₂O: 10 M at 20 °C, clear, colorless

form 

Solid

color 

White

Odor

Slight formic acid odour

PH Range

6 - 7

PH

6.53(1 mM solution);6.5(10 mM solution);6.49(100 mM solution);6.45(1000 mM solution)

Water Solubility 

soluble

Sensitive 

Hygroscopic

λmax

λ: 260 nm Amax: 0.05
λ: 280 nm Amax: 0.04

Merck 

14,523

BRN 

3625095

Stability:

Stable. Hygroscopic. Incompatible with strong acids, strong oxidizing agents.

InChIKey

VZTDIZULWFCMLS-UHFFFAOYSA-N

LogP

-3.34 at 25℃

CAS DataBase Reference

540-69-2(CAS DataBase Reference)

EPA Substance Registry System

Ammonium 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

F 

3-10

TSCA 

Yes

HS Code 

29151200

Hazardous Substances Data

540-69-2(Hazardous Substances Data)

Toxicity

LD50 orl-mus: 2250 mg/kg ZERNAL 9,332,69

MSDS

• Language:English Provider:Ammonium formate
• Language:English Provider:SigmaAldrich
• Language:English Provider:ACROS
• Language:English Provider:ALFA

Ammonium formate Usage And Synthesis

Chemical Properties

Ammonium 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) does a fairly good job of filling the gap at the low-pH end.

Physical properties

White 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.

Uses

Ammonium 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.

Uses

Pure 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.

Reactions

When 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 Reactions

Ammonium formate is generally soluble in water. 

Reactivity Profile

Salts, 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 Hazard

Inhalation causes irritation of nose and throat. Ingestion irritates mouth and stomach. Contact with eyes or skin causes irritation.

Fire Hazard

Special Hazards of Combustion Products: Toxic and irritating ammonia and formic acid gases may form in fire.

Safety Profile

Moderately toxic by ingestion andintravenous routes. When heated to decomposition itemits toxic fumes of NOx and NH3.

Purification Methods

Heat 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] 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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