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What Is Ammonium Formate?
Ammonium formate (NH₄HCO₂) is the ammonium salt of formic acid. It appears as white monoclinic deliquescent crystals or granules with a slight odor of ammonia. First synthesized in the 19th century, it has evolved from a laboratory curiosity into an essential chemical intermediate used globally.
Key identifiers:
Property | Value |
CAS Number | 540-69-2 |
Molecular Formula | CHO₂·NH₄ (or NH₄HCO₂) |
Molecular Weight | 63.06 g/mol |
EINECS Number | 208-753-9 |
UN Number | Not classified as dangerous goods for transport |
HS Code | 2915.12 |
Ammonium formate is produced by reacting formic acid with ammonia, yielding a highly water-soluble salt that finds use wherever a volatile, nitrogen-rich formate source is needed.
Understanding the physical behavior of ammonium formate is critical for storage, handling, and process design.
Property | Specification |
Appearance | White crystalline solid or granules |
Density | 1.280 g/cm³ |
Melting Point | 116 °C (241 °F) |
Water Solubility | 102 g/100 mL at 20 °C |
pH (5% aqueous solution) | 5.5–6.5 (slightly acidic) |
Hygroscopicity | Deliquescent — absorbs moisture readily |
Decomposition | Decomposes into formamide + H₂O upon heating above melting point |
Ammonium formate serves a broad range of industrial sectors. Below are its primary non-pharmaceutical applications:
Application Area | Role of Ammonium Formate |
Organic Synthesis | N-formylating agent, hydrogen donor, reductive amination reagent |
Formamide Production | Thermal decomposition feedstock |
Analytical Chemistry | Volatile buffer for HPLC and LC-MS mobile phases |
Animal Nutrition | Feed acidifying agent (FDA-approved for swine) |
Deicing | Formate-based runway and pavement deicers |
Leather & Textile | pH adjustment and process chemical |
Pd/C Catalytic Reduction | Hydrogen source for alkene/functional group reduction |
Low cost relative to alternatives
● — competitive pricing compared to other formate salts
Volatility
● — decomposes cleanly without leaving non-volatile residues (critical for LC-MS)
Dual functionality
● — acts as both a formylating agent and a reducing agent
Environmental profile
● — formate-based products have lower environmental persistence than urea or acetate alternatives
One of the highest-value applications of ammonium formate is as a mobile phase buffer/modifier in high-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS).
When HPLC is coupled with mass spectrometry, the mobile phase must be volatile — non-volatile buffers like phosphate or citrate would precipitate in the ion source and foul the instrument. Ammonium formate decomposes into volatile NH₃ and formic acid under MS conditions, making it one of the go-to choices for LC-MS-compatible separations.
Typical conditions:
● Concentration range:
5–50 mM
● pH range:
3.0–6.0
(often paired with formic acid for pH control)
● Common column types: C18, HILIC, ion-exchange
Ammonium formate improves:
Peak symmetry
● for basic compounds
Ionization efficiency
● in electrospray ionization (ESI)
Retention time reproducibility
● across runs
Baseline stability
● in gradient elution
For analytical work, always use LC-MS grade ammonium formate to minimize background signal and column contamination:
Purity Requirement | Typical Value |
Assay | ≥ 99.0% |
UV Absorbance (210 nm) | ≤ 0.05 AU |
Metals (Na, K, Fe) | ≤ 5 ppm each |
Insoluble matter | ≤ 0.01% |
The U.S. FDA recognizes ammonium formate as a feed acidifying agent under 21 CFR 573.170, specifically for use in complete swine feeds at levels not exceeding 1.2% of the total ration.
Benefits in swine nutrition:
● Lowers gastrointestinal pH, inhibiting pathogenic bacteria
● Improves feed digestibility and nutrient absorption
● Supports growth performance in weaning piglets
● Acts as a non-antibiotic growth promoter alternative
While not a direct fertilizer, ammonium formate contributes nitrogen in a form that can be utilized in certain controlled-release or specialty nutrient formulations. Its role is primarily as a feed additive rather than a soil-applied product.
Ammonium formate is available in multiple grades depending on the end-use requirements:
Grade | Typical Purity | Primary Use |
Technical Grade | ≥ 97% | Formamide production, feed additive, general synthesis |
Reagent Grade | ≥ 98.5% | Laboratory synthesis, general analytical work |
HPLC/LC-MS Grade | ≥ 99.0% | Chromatography mobile phases |
ACS Grade | ≥ 99.0% | Analytical applications per ACS specifications |
Ammonium formate is used in organic synthesis (Leuckart reaction, N-formylation), as a volatile buffer in HPLC/LC-MS, in formamide production, as an animal feed acidifier, and in deicing formulations.
Yes, ammonium formate is highly soluble in water — approximately 102 g per 100 mL at 20 °C, forming a clear, slightly acidic solution.
When heated above its melting point (116 °C), ammonium formate decomposes into formamide (HCONH₂) and water. This is its primary industrial reaction pathway.
The CAS number for ammonium formate is 540-69-2.
Ammonium formate is not classified as hazardous under GHS. However, standard laboratory handling precautions should be observed, including gloves and eye protection. It is not classified as a carcinogen by IARC.
Both are volatile buffers suitable for LC-MS, but ammonium formate is more acidic (pH ~3–4 with formic acid) and preferred for acidic separations. Ammonium acetate buffers at pH ~4–5.5. Choice depends on the analyte pKa and column chemistry.
Yes, it is FDA-approved under 21 CFR 573.170 as a feed acidifying agent for complete swine feeds at levels up to 1.2% of the ration.
When stored in a cool, dry environment in tightly sealed containers, ammonium formate typically has a shelf life of 24 months. Due to its deliquescent nature, exposure to humidity should be minimized.
Store in a cool (15–25 °C), dry, well-ventilated area in tightly sealed containers. HDPE drums or PE-lined kraft paper bags are standard for bulk packaging.
