Ammonium nitrate is a chemical compound with the formula . It is a white crystalline salt consisting of of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, but does not form hydrates. It is predominantly used in agriculture as a high-nitrogen fertilizer.
Its other major use is as a component of explosive mixtures used in mining, quarrying, and civil construction. It is the major constituent of ANFO, an industrial explosive which accounts for 80% of explosives used in North America; similar formulations have been used in improvised explosive devices.
Many countries are phasing out its use in consumer applications due to concerns over its potential for misuse.[ Ammonium nitrate sold by ton as U.S. regulation is stymied. – The Dallas Morning News] Accidental ammonium nitrate explosions have killed thousands of people since the early 20th century.
Occurrence
Ammonium nitrate is found as the natural mineral
gwihabaite (formerly known as nitrammite)
– the ammonium analogue of
nitre (mineralogical name: niter)
– in the driest regions of the
Atacama Desert in
Chile, often as a crust on the ground or in conjunction with other nitrate,
iodate, and
halide minerals. Ammonium nitrate was mined there until the
Haber process made it possible to synthesize nitrates from atmospheric nitrogen, rendering nitrate mining obsolete.
Production, reactions and crystalline phases
The industrial production of ammonium nitrate entails the acid-base reaction of
ammonia with
nitric acid:
- HNO3 + NH3 → NH4NO3
The ammonia required for this process is obtained by the
Haber process from nitrogen and hydrogen. Ammonia produced by the Haber process can be oxidized to nitric acid by the
Ostwald process. Ammonia is used in its
anhydrous form (a gas) and the nitric acid is concentrated. The reaction is violent owing to its highly
exothermic nature. After the solution is formed, typically at about 83% concentration, the excess water is evaporated off to leave an ammonium nitrate (AN) content of 95% to 99.9% concentration (AN melt), depending on grade. The AN melt is then made into "prills" or small beads in a
spray tower, or into granules by spraying and tumbling in a rotating drum. The prills or granules may be further dried, cooled, and then coated to prevent caking. These prills or granules are the typical AN products in commerce.
Another production method is a variant of the nitrophosphate process:
- calcium nitrate + ammonia + carbon dioxide + H2O → 2 NH4NO3 + CaCO3
The products, calcium carbonate and ammonium nitrate, may be separately purified or sold combined as calcium ammonium nitrate.
Ammonium nitrate can also be made via metathesis reactions:
- ammonium sulfate + barium nitrate → 2 NH4NO3 + barium sulfate
- Ammonium sulfate + Calcium nitrate → 2 NH4NO3 + Calcium sulfate
- NH4Cl + silver nitrate → NH4NO3 + silver chloride
Reactions
As ammonium nitrate is a salt, both the cation, , and the anion, , may take part in chemical reactions.
Solid ammonium nitrate decomposes on heating. At temperatures below around 300 °C, the decomposition mainly produces nitrous oxide and water:
- NH4NO3 → N2O + 2 H2O
At higher temperatures, the following reaction predominates.
- 2 NH4NO3 → 2 N2 + O2 + 4 H2O
Both decomposition reactions are exothermic and their products are gases. Under certain conditions, this can lead to a runaway reaction, with the decomposition process becoming explosive.
The red–orange colour in an explosion cloud is due to nitrogen dioxide, a secondary reaction product.
Crystalline phases
Several crystalline phases of ammonium nitrate have been observed. The following occur under atmospheric pressure.
> |
|
| (liquid) | (above 169.6) | |
| I | 169.6 to 125.2 | cubic |
| II | 125.2 to 84.2 | tetragonal |
| III | 84.2 to 32.3 | α-rhombic |
| IV | 32.3 to −16.8 | β-rhombic |
| V | below −16.8 | tetragonal |
The transition between β-rhombic to α-rhombic forms (at 32.3 °C) occurs at ambient temperature in many parts of the world. These forms have a 3.6% difference in density and hence transition between them causes a change in volume. One practical consequence of this is that ammonium nitrate cannot be used as a solid rocket motor propellant, as it develops cracks. Stabilized ammonium nitrate (PSAN) was developed as a solution to this and incorporates metal halides stabilisers, which prevent density fluctuations.
Applications
Fertilizer
Ammonium nitrate is an important fertilizer with NPK rating 34-0-0 (34% nitrogen).
Explosives
Ammonium nitrate readily forms explosive mixtures with varying properties when combined with explosives such as TNT or with fuels like aluminium powder or fuel oil.
Examples of explosives containing ammonium nitrate include:
Mixture with fuel oil
ANFO is a mixture of 94% ammonium nitrate ("AN") and 6% fuel oil ("FO") widely used as a bulk industrial explosive.[
]
Terrorism
Ammonium nitrate-based explosives were used in the Sterling Hall bombing in Madison, Wisconsin, 1970, the Oklahoma City bombing in 1995, the 2011 Delhi bombings, the 2011 bombing in Oslo, the Myyrmanni bombing and the 2013 Hyderabad blasts.
In November 2009, the government of the KPK (previously termed as NWFP) of Pakistan imposed a ban on ammonium sulfate, ammonium nitrate, and calcium ammonium nitrate fertilizers in the former Malakand Divisioncomprising the Upper Dir, Lower Dir, Swat, Chitral, and Malakand districts of the NWFP – following reports that those chemicals were used by militants to make explosives. Due to these bans, "Potassium chloratethe material which allows safety matches to catch firehas surpassed fertilizer as the explosive of choice for insurgents."
Niche uses
Ammonium nitrate is used in some instant cold packs, as its dissolution in water is highly endothermic. In 2021, King Abdullah University of Science and Technology in Saudi Arabia conducted experiments to study the potential for dissolving ammonium nitrate in water for off-grid cooling systems and as a refrigerant. They suggested that the water could be distilled and reused using solar energy to avoid water wastage in severe environments.
It was once used, in combination with independently explosive "fuels" such as guanidine nitrate,[ Airbag Compound Has Vexed Takata for Years – The New York Times] as a cheaper (but less stable) alternative to 5-aminotetrazole in the inflators of manufactured by Takata Corporation, which were recalled as unsafe after killing 14 people.[ A Cheaper Airbag, and Takata's Road to a Deadly Crisis. – The New York Times] The current USA death total is 27.
Safety, handling, and storage
Numerous safety guidelines are available for storing and handling ammonium nitrate. Health and safety data are shown on the safety data sheets available from suppliers and from various governments.[ Chemical Advisory: Safe Storage, Handling, and Management of Ammonium Nitrate United States Environmental Protection Agency]
Pure ammonium nitrate does not burn, but as a strong oxidizer, it supports and accelerates the combustion of organic (and some inorganic) material.
While ammonium nitrate is stable at ambient temperature and pressure under many conditions, it may detonate from a strong initiation charge. It should not be stored near high explosives or blasting agents.
Molten ammonium nitrate is very sensitive to shock and detonation, particularly if it becomes contaminated with incompatible materials such as combustibles, flammable liquids, acids, chlorates, chlorides, sulfur, metals, charcoal and sawdust.
Contact with certain substances such as chlorate, mineral acid and metal sulfide, can lead to vigorous or even violent decomposition capable of igniting nearby combustible material or detonating.
Ammonium nitrate begins decomposition after melting, releasing NOx, Nitric acid, Ammonia and Water. It should not be heated in a confined space.
Ammonium nitrate has a critical relative humidity of 59.4% at 30 °C. At higher humidity it will absorb moisture from the atmosphere. Therefore, it is important to store ammonium nitrate in a tightly sealed container. Otherwise, it can coalesce into a large, solid mass. Ammonium nitrate can absorb enough moisture to liquefy. Blending ammonium nitrate with certain other fertilizers can lower the critical relative humidity.
The potential for use of the material as an explosive has prompted regulatory measures. For example, in Australia, the Dangerous Goods Regulations came into effect in August 2005 to enforce licensing in dealing with such substances.[Ammonium Nitrate-Regulating its use, Balancing Access & Protection from ] Additional uses such as education and research purposes may also be considered, but individual use will not. Employees of those with licenses to deal with the substance are still required to be supervised by authorized personnel and are required to pass a security and national police check before a license may be granted.
Health hazards
Ammonium nitrate is not hazardous to health and is usually used in fertilizer products.
Ammonium nitrate has an LD50 of 2217 mg/kg,
Disasters
Ammonium nitrate decomposes, non-explosively, into the nitrous oxide and water vapor when heated. However, it can be induced to decompose explosively by detonation.
Ammonium nitrate can explode through two mechanisms:
-
Shock induced detonation. An explosive charge within or in contact with a mass of ammonium nitrate causes the ammonium nitrate to detonate. Examples of such disasters are Kriewald, Morgan (present-day Sayreville, New Jersey), Oppau explosion, and Tessenderlo.
-
Deflagration to detonation transition. The ammonium nitrate explosion results from a fire that spreads into the ammonium nitrate (Texas City, TX; Brest; West, TX; Tianjin; Beirut), or from ammonium nitrate mixing with a combustible material during the fire (Gibbstown, Cherokee, Nadadores). The fire must be confined at least to a degree for successful transition from a fire to an explosion.
See also
Sources
-
Properties: UNIDO and International Fertilizer Development Center (1998), Fertilizer Manual, Kluwer Academic Publishers, .
External links
