Ammonium nitrate

Ammonium nitrate

Names
IUPAC name Ammonium nitrate
Identifiers
CAS Registry Number	6484-52-2 Y
ChemSpider	21511 Y
InChI InChI=1S/NO3.H3N/c2-1(3)4;/h;1H3/q-1;/p+1 Y Key: DVARTQFDIMZBAA-UHFFFAOYSA-O Y InChI=1/NO3.H3N/c2-1(3)4;/h;1H3/q-1;/p+1 Key: DVARTQFDIMZBAA-IKLDFBCSAH
Jmol-3D images	Image
RTECS number	BR9050000
SMILES [O-][N+]([O-])=O.[NH4+]
UNII	T8YA51M7Y6 Y
UN number	0222 – with > 0.2% combustible substances 1942 – with <= 0.2% combustible substances 2067 – fertilizers 2426 – liquid
Properties
Chemical formula	(NH4)(NO3)
Molar mass	80.052 g/mol
Appearance	white/grey solid
Density	1.725 g/cm3 (20 °C)
Melting point	169.6 °C (337.3 °F; 442.8 K)
Boiling point	approx. 210 °C;decomposes
Solubility in water	118 g/100 ml (0 °C) 150 g/100 ml (20 °C) 297 g/100 ml (40 °C) 410 g/100 ml (60 °C) 576 g/100 ml (80 °C) 1024 g/100 ml (100 °C)[1]
Structure
Crystal structure	trigonal
Explosive data
Shock sensitivity	very low
Friction sensitivity	very low
Detonation velocity	5270 m/s
Hazards
MSDS	ICSC 0216
Main hazards	Explosive
EU Index	not listed
EU classification	E (E)
NFPA 704	0 2 3 OX
LD50 (Median lethal dose)	2085–5300 mg/kg (oral in rats, mice)[2]
Related compounds
Other anions	Ammonium nitrite
Other cations	Sodium nitrate Potassium nitrate Hydroxylammonium nitrate
Related compounds	Ammonium perchlorate
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

The chemical compound ammonium nitrate, the nitrate salt of ammonium, has the chemical formula NH₄NO₃, simplified to N₂H₄O₃. It is a white crystalline solid which is highly soluble in water. It is predominantly used in agriculture as a high-nitrogen fertilizer.^[3] The compound is used as an explosive in mining, and also sometimes in improvised explosive devices. It is the main component of ANFO, a popular explosive, which accounts for 80% of explosives used in North America. It is used in instant cold packs, as hydrating the salt is an endothermic process.

Ammonium nitrate is found as a natural mineral (ammonia nitre—the ammonium analogue of saltpetre and other nitre minerals such as sodium nitrate) in the driest regions of the Atacama Desert in Chile, often as a crust on the ground and/or in conjunction with other nitrate, chlorate, iodate, and halide minerals. Ammonium nitrate was mined there in the past, but virtually 100% of the chemical now used is synthetic.

Fertilizer

Ammonium nitrate is an important fertilizer with the NPK rating 34-0-0 (34% nitrogen).^[4] It is less concentrated than urea (46-0-0), giving ammonium nitrate a slight transportation disadvantage. Ammonium nitrate's advantage over urea is that it is more stable and does not lose nitrogen to the atmosphere. During warm weather it is best to apply urea soon before rain is expected to minimize nitrogen loss.^[5][6]

Safety, handling, and storage

Health and safety data are shown on the material safety data sheets available from suppliers and found on the internet.^[7] In response to several explosions resulting in the deaths of numerous people, U.S. agencies of Environmental Protection (EPA), Occupational Health and Safety (OSHA) and the Bureau of Alcohol, Tobacco and Firearms jointly issued safety guidelines.^[8]

Heating or any ignition source may cause violent combustion or explosion.^[9] Ammonium nitrate reacts with combustible and reducing materials as it is a strong oxidant. Although it is mainly used for fertilizer, it can be used for explosives. It was sometimes used to blast away earth to make farm ponds.^[10][11] Ammonium nitrate is also used to modify the detonation rate of other explosives, such as ammonia-based dynamites, for example nitroglycerin and amatol.

Numerous safety guidelines are available for storing and handling ammonium nitrate.^[12] It should not be stored near combustible substances.

Ammonium nitrate has a critical relative humidity of 59.4%, above which 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.^[13]

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.^[14] Licenses are granted only to applicants (industry) with appropriate security measures in place to prevent any misuse.^[15] 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.

Production

The industrial production of ammonium nitrate entails the acid-base reaction of ammonia with nitric acid:^[16]

HNO₃ + NH₃ → NH₄NO₃

Ammonia is used in its anhydrous form (i.e. gas form) and the nitric acid is concentrated. This reaction is violent owing to its highly exothermic nature. After the solution is formed, typically at about 83% concentration, the excess water is evaporated to 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.

The ammonia required for this process is obtained by the Haber process from nitrogen and hydrogen. Ammonia produced by the Haber process is oxidized to nitric acid. Another production method is used in the so-called Odda process.

Ammonium nitrate can also be made via metathesis reactions:

(NH₄)₂SO₄ + 2 NaNO₃ → 2 NH₄NO₃ + Na₂SO₄

(NH₄)₂SO₄ + Ca(NO₃)₂ → 2 NH₄NO₃ + CaSO₄

Sodium sulfate is removed by lowering the temperature of the mixture. Since sodium sulfate is much less water-soluble than ammonium nitrate, it precipitates, and may be filtered off. For the reaction with calcium nitrate, the calcium sulfate generated is quite insoluble, even at room temperature.

Reactions

Ammonium nitrate reacts with metal hydroxides, releasing ammonia and forming alkali metal nitrate:

NH₄NO₃ + MOH → NH₃ + H₂O + MNO₃ (M = Na, K)

Ammonium nitrate gives ammonium chloride and nitric acid upon reaction with hydrochloric acid:

NH₄NO₃ + HCl → NH₄Cl + HNO₃

Ammonium nitrate leaves no residue when heated:

NH₄NO₃ → N₂O + 2H₂O

Ammonium nitrate is also formed in the atmosphere from emissions of NO, SO₂, and NH₃, and is a secondary component of PM10.^[17]

Crystalline phases

Transformations of the crystal states due to changing conditions (temperature, pressure) affect the physical properties of ammonium nitrate. These crystalline states have been identified:

System	Temperature (°C)	State	Volume change (%)
	> 169.6	liquid
I	169.6 to 125.2	cubic	+2.1
II	125.2 to 84.2	tetragonal	−1.3
III	84.2 to 32.3	α-rhombic	+3.6
IV	32.3 to −16.8	β-rhombic	−2.9
V	−16.8	tetragonal

The type V crystal is a quasicubic form which is related to caesium chloride, the nitrogen atoms of the nitrate anions and the ammonium cations are at the sites in a cubic array where Cs and Cl would be in the CsCl lattice.^[18]

Health hazards

Health and safety data are shown on the material safety data sheets which are available from suppliers and can be found on the internet.^[19]

Ammonium nitrate is not very hazardous to health and is usually used in fertilizer products.^[19][20][21] The chances of direct personal exposure to the chemical are very low, because the fertilization of the soil by use of ammonium nitrate is done at early stages of plant growth and usually does not remain detectable on the harvested plants or when the plants reach the consumer.

Ammonium nitrate has an LD₅₀ of 2217 mg/kg,^[19] which for comparison is about two-thirds that of table salt.

Acute health effects

Short-term exposure to ammonium nitrate can cause symptoms ranging from minor irritation to nausea, vomiting, gastric irritation, headaches, dizziness, and hypertension.^[22]

Area of exposure	Hazard level
Ingestion	Moderately hazardous
Skin contact	Moderately hazardous (irritant)
Eye contact	Moderately hazardous
Inhalation	Moderately hazardous

Long-term health effects

The toxicity of nitrates when ingested is due to in vivo conversion to nitrites. The material safety data sheet considers chronic ingestion of more than 5 mg/kg/day unacceptable. The primary overdose effects of chronic exposure are orthostatic hypotension and methemoglobinemia. Other common effects include: faintness, fatigue, weakness, depression, mental impairment, dizziness, shortness of breath, and reflex tachycardia; headache, nausea, vomiting, and nephritis may also occur.^[19]

Types of effect	Effect level
Carcinogenic effects	Though no ammonium nitrate-specific studies are available, nitrates can be reduced to nitrites in the body, and the formed nitrites can subsequently react with amines to form N-nitrosamines, a class of chemicals suspected to be carcinogens.[19]
Mutagenic effects	In general, nitrates and nitrites are genotoxic.[19]
Teratogenic effects	None
Developmental toxicity	Though not specific to ammonium nitrate, some studies have shown a link between birth defects (particularly neural tube defects) and nitrate-contaminated well water.
Prolonged exposure	Causes damage to lungs and mucous membranes and may also cause damage to blood and gastrointestinal tract. Chronic ingestion may also cause nephritis.[19]

Disasters

Ammonium nitrate decomposes into the gases nitrous oxide and water vapor when heated (not an explosive reaction); however, it can be induced to decompose explosively by detonation. Large stockpiles of the material can be a major fire risk due to their supporting oxidation, and may also detonate, as happened in the Texas City disaster of 1947, which led to major changes in the regulations for storage and handling.

The two major classes of incidents resulting in explosions are:

• The explosion happens by the mechanism of shock-to-detonation transition. The initiation happens by an explosive charge going off in the mass, by the detonation of a shell thrown into the mass, or by detonation of an explosive mixture in contact with the mass. The examples are Kriewald, Morgan (present-day Sayreville, New Jersey), Oppau, and Tessenderlo.

• The explosion results from a fire that spreads into the ammonium nitrate itself (Texas City, Brest, Oakdale PA), or from a mixture of ammonium nitrate with a combustible material during the fire (Repauno, Cherokee, Nadadores). The fire must be confined at least to a degree for successful transition from a fire to an explosion (a phenomenon known as "deflagration-to-detonation transition"). Pure, compact AN is stable and very difficult to ignite, and numerous cases exist when even impure AN did not explode in a fire.

Ammonium nitrate-based explosives were used in the Oklahoma City and 2011 Delhi bombings, the 2013 Hyderabad blasts, and the bombing in Oslo 2011.

Ammonium nitrate decomposes in temperatures normally well above 200°C. However, the presence of impurities (organic and/or inorganic) often reduce the temperature point when heat is being generated. Once the AN has started to decompose, then a runaway reaction will normally occur as the heat of decomposition is very large. AN evolves so much heat that this runaway reaction is normally impossible to stop. This is a well-known hazard with some types of N-P-K Fertilizers, and it is responsible for the loss of several cargo ships.

Under normal handling conditions, ammonium nitrate is not harmful. However, inhalation of high concentrations of its dust can cause respiratory tract irritation. Symptoms may include: coughing, sore throat, shortness of breath, or even suffocation. When swallowed in high concentrations, ammonium nitrate may cause headache, dizziness, abdominal pain, vomiting, bloody diarrhea, weakness, a tingling sensation, heart and circulation irregularities, convulsions, collapse, and suffocation. It forms a mild acid when mixed with water. This acid can cause irritation to the eyes, nose, and skin.^[23]

In November 2009, a ban on ammonium sulfate, ammonium nitrate, and calcium ammonium nitrate fertilizers was imposed in the former Malakand Division—comprising the Upper Dir, Lower Dir, Swat, Chitral, and Malakand districts of the North West Frontier Province (NWFP) of Pakistan—by the NWFP government, following reports that those chemicals were used by militants to make explosives. In January 2010, these substances were also banned in Afghanistan for the same reason. After several cases, AN has now been legalised due to the Pakistani forces of NWFP.

Ammonium nitrate was suspected as the explosive responsible for the fertilizer plant explosion in West, Texas on April 17, 2013. Investigators said they believe it exploded following a fire that began in the plant's office.^[24]

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.^[25]:1 It is used in coal mining, quarrying, metal mining, and civil construction in undemanding applications where the advantages of ANFO's low cost and ease of use matter more than the benefits offered by conventional industrial explosives, such as water resistance, oxygen balance, high detonation velocity, and performance in small diameters.^[25]:2

References

External links

• International Chemical Safety Card 0216
• "Storing and Handling Ammonium Nitrate", United Kingdom Health and Safety Executive publication INDG230 (1986)
• Chemical Advisory: Safe Storage, Handling, and Management of Ammonium Nitrate United States Environmental Protection Agency
• Calculators: surface tensions, and densities, molarities and molalities of aqueous ammonium nitrate

Salts and the ester of the Nitrate ion
HNO3																	He
LiNO3	Be(NO3)2											B(NO3)4−	RONO2	NO3− NH4NO3	O	FNO3	Ne
NaNO3	Mg(NO3)2											Al(NO3)3	Si	P	S	ClONO2	Ar
KNO3	Ca(NO3)2	Sc(NO3)3	Ti(NO3)4	VO(NO3)3	Cr(NO3)3	Mn(NO3)2	Fe(NO3)3	Co(NO3)2, Co(NO3)3	Ni(NO3)2	Cu(NO3)2	Zn(NO3)2	Ga(NO3)3	Ge	As	Se	Br	Kr
RbNO3	Sr(NO3)2	Y	Zr(NO3)4	Nb	Mo	Tc	Ru	Rh	Pd(NO3)2	AgNO3	Cd(NO3)2	In	Sn	Sb	Te	I	XeFNO3
CsNO3	Ba(NO3)2		Hf	Ta	W	Re	Os	Ir	Pt	Au	Hg2(NO3)2, Hg(NO3)2	Tl(NO3)3	Pb(NO3)2	Bi(NO3)3	Po	At	Rn
Fr	Ra		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Uut	Fl	Uup	Lv	Uus	Uuo
		↓
		La	Ce(NO3)x	Pr	Nd	Pm	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu
		Ac	Th	Pa	UO2(NO3)2	Np	Pu	Am	Cm	Bk	Cf	Es	Fm	Md	No	Lr