HAZMAT Articles

Ammonium Nitrate
Introduction Ammonium nitrate is one of the more important chemicals produced worldwide. It is primarily used as a fertiliser; however it is better known for its use as an ingredient in explosives, especially in mining. It is also used in a minor way, in solid fuel propellants for rockets, and in the manufacture of laughing gas. Structure Ammonium nitrate has the formula (NH4NO3). The ammonium ion with its positive charge, is held in position by the negatively charged nitrate ion. The ammonium ion consists of a nitrogen atom, bonded to four hydrogen atoms, arranged in space at the corners of a tetrahedron. Nitrate on the other hand is flat, with a nitrogen atom in the middle, and bonded to three oxygen atoms at the corners of a triangle. One way in which they are all held together is as follows:1 Agriculture As a fertiliser, ammonium nitrate will continue to be used for a good while to come. The reason is that nitrogen is present as ammonium and nitrate. Plant prefer to take up nitrate through their roots and use it to grow. On the other hand, nitrate can be easily leached away from the root zone by too much water, because it does not bind to the soil particles. Ammonium on the other hand tends to be bound tightly to soil particles, so it isnt easily washed away. It can then converted to nitrate by soil bacteria, and so also become available for plant growth. In this way it behaves like two applications of fertiliser for the price of one. Manufacture The manufacture of ammonium nitrate is described as 2 relatively simple, but technologically challenging. It involves a neutralisation reaction between ammonia and nitric acid; a reaction that is both violent and very exothermic. HNO3 (aqueous) + NH3 (gas) NH4NO3 (aqueous) Upon completion, the excess water is evaporated to form small spherical prills, which are about 2 mm diameter. Finally, these prills are coated to prevent caking with about 0.5% diatomaceous earth. Properties CAS Appearance Solubility Melting point Boiling point

6484-52-2 White solid 150 gm/100 mL at 20 deg C 170 deg C ~210 deg C decomposes

Ammonium nitrate structure (Nitrogen Blue, Oxygen Red, Hydrogen White) Ammonium nitrate, depending on its temperature, can assume five different crystalline forms. This means there are five possible alignments of the tetrahedra and triangles to make up these crystalline structures. It also has to expand or contract to meet the space requirements for these structures.
20th January 2010

Ammonium nitrate is a white crystalline powder. If left standing in the open, it will absorb moisture from the air (hygroscopic); not enough to turn it into a liquid, but enough for it to cake into a solid mass, which is extremely difficult to break up. It is also extremely soluble in water; it dissolves endothermically, so that the final solution feels quite cold. It can be used to prepare freezing mixtures. It is an oxidiser, and therefore becomes an oxygen source during combustion. Under these conditions, it will also release nitrogen oxides which are extremely toxic. However, of much greater concern is the potential for ammonium nitrate to explode.

Page 1

As an explosive In pure form, ammonium nitrate is not classified as an explosive, because it is so difficult to detonate. Sparks, fire or friction will not set it off. The presence of certain impurities however, will increase its sensitivity to shock. Even when prepared as an explosive mixture for blasting, it still requires detonation to set it off. Such mixtures have the explosive power of about 50% TNT.3 When heated to about 200 230 deg. C, it undergoes an exothermic reaction which can be controlled to produce nitrous oxide (or laughing gas) NH4NO3 (aqueous) N2O + 2H2O However, at higher temperatures exothermic detonation can occur. another final

Slight changes which made the risk to climb imperceptibly. It is a warning that vigilance is always required, and even when small changes are introduced into a process, past practices are no guide to present actions. It was this explosion that lead to the development of coated to prills to stop caking. However the coating at the time was organically based and consisted of 1% composition of paraffin, resin and vaseline.8 Texas City Unfortunately this is not the end of the story. Even association with combustibles can be hazardous. In 1947, Texas City, a fire started in a ships hold carrying 2,300 tonnes of ammonium nitrate. It was packaged in sacks consisting of 6 layers of paper, two of which were water-proofed with bitumen.9 In an attempt to save the cargo, the hatches were closed and steam valves opened, to try and smother the flames. However, after a few minutes, the hatch covers blew off and dense quantities of orange-red 10 smoke were released. Then after about an hour, the ship exploded, killing the captain, his crew of 32, and hundreds of others who had gathered at the wharf to watch, and four people circling in two aircraft overhead. It caused major fires in the giant chemical works that was nearby, including 20 bulk tanks containing light hydrocarbons through to heavy oils, as well as a bulk sulphur storage. The next day a second ship also carrying ammonium nitrate, and which had also caught fire from the initial explosion, also blew up. There were 468 fatalities, 100 were listed as missing, and 3,000 were injured. Dangerous Goods Ammonium nitrate can only be transported as a pure chemical, in which there is no possibility of contamination, or potential to cake. The following list of UN numbers is in order they may be encountered in Western Australia. Some the UN shipping names take the form of a specification, in which the product must comply with all the requirements. UN 1942
AMMONIUM NITRATE, with not more than 0.2% total combustible material, including any organic substance, calculated as carbon to the exclusion of any other added substance

NH4NO3 2N2 + 4H2O + O2 Past failures The first recorded explosion of ammonium nitrate involved seven kilograms, and occurred in London in 4 1896. However, from that point it took several major disasters, before the hazards associated with ammonium nitrate were fully appreciated, and which has led to todays standard of manufacture, transportation and storage. For example, it was standard practice to use explosives to break up bulk ammonium nitrate that had caked into a solid mass. The first major lesson this was not a good idea occurred in 1921, in Upper Silesia in Germany, when a rail wagon load of ammonium nitrate blew up after explosives were used. It also set off the neighbouring wagon, to involve a total of 30 tonnes of ammonium nitrate, that left a 20 metre hole in the ground.5 Oppau Unfortunately in the same year at Oppau, again in Germany, 4,500 tonnes of ammonium nitrate blew up when explosives were again used. The explosion killed 561 people, including four in a town seven kilometres away, and left a crater 75 by 115 by 10 6 metres deep. Up to the day of the accident, there had been more 7 than 20,000 blastings without effect. While the Upper Selisia explosion involved pure ammonium nitrate, this product was a 50/50 mixture of ammonium sulphate and nitrate, which on the basis of testing the manufacturer had concluded was not liable to explode. However on further testing, they found it could explode if the product had a low density. They also found the explosive sensitivity dramatically increased if the proportion of nitrate exceeded 60%. Finally, slight changes in their production process had resulted in a product with lower moisture content in which the nitrate composition was also a lot more variable.
20th January 2010

OXIDIZING AGENT

Class Hazchem

5.1 1Z

5.1

If testing reveals more than 0.2% of combustible material present, then the product must be allocated UN 0222 and transported as an explosive, Class 1.1D

Page 2

UN 3375
AMMONIUM NITRATE EMULSION, intermediate for blasting explosives, or AMMONIUM NITRATE GEL, intermediate for blasting explosives, or AMMONIUM NITRATE SUSPENSION, intermediate for blasting explosives

OXIDIZING AGENT

5.1

Class Hazchem UN 2426

5.1 1Y

AMMONIUM NITRATE, LIQUID (hot concentrated solution)

when a workman cut into metal ducting of the 11 extraction system from the animal rooms. A deposit in the ducting was ignited, and the fire rapidly spread throughout the whole complex, causing five million dollars damage. This deposit had slowly formed over many years, from ozone gas that was added to the effluent gases, from the animal rooms to neutralize odours. It was found that ozone reacted with ammonia, from the animal urine, to form ammonium nitrate which had deposited on the ducting walls, together with a lot of other organic by-products from the animals. It was a fire was just waiting to happen.

Class 5.1 5.1 Hazchem 1Y In WA, it is transported at 135 140 degs C as a 90% solution. UN 2067
AMMONIUM NITRATE BASED FERTLIZER
OXIDIZING AGENT
1

OXIDIZING AGENT

Class Hazchem UN 2071

5.1 1Z

5.1

AMMONIUM NITRATE BASED FERTLIZER

Class Hazchem

9 1Z

MISCELLANEOUS DANGEROUS GOODS

Further UN numbers are allocated for AMMONIUM NITRATE EXPLOSIVE (UN 0082 & 0331) both as Class 1.1D Security Issues Because ammonium nitrate has been used in terrorist / criminal actions, a further layer of regulation has been applied to its use. In WA, the Dangerous Goods Safety (Security Risk Substances) Regulations 2007, requires strict accountability of all those who intend using ammonium nitrate, whether in mining or in agriculture. Storage Ammonium nitrate must be stored dry, kept well ventilated and away from any sources of heat. It must not be stored with any combustible material, metal powders or explosives. In conclusion Even today ammonium nitrate continues to be the cause of explosions. A useful list can be found at
http://en.wikipedia.org/wiki/Ammonium_nitrate_disasters

http://en.wikipedia.org/wiki/Ammonium_nitrate, accessed 5th Jan 2010 2 http://en.wikipedia.org/wiki/Ammonium_nitrate, accessed 5th Jan 2010 3 Seidel A, Kirk-Othmer Encyclopedia of Chemical Technology, 5th Ed. 2004, John Wiley & Sons, Hoboken, NJ. 4 Marshall VC, Major Chemical Hazards, 1987, Ellis Horwood, England 5 Medard LA, Accidental Explosions, Vol 2, Types of Explosive Substances, 1989, Ellis Horwood, England 6 Marshall 7 Medard 8 Medard 9 Medard 10 Lygate JF, Rushbrooks Fire Aboard, 3rd ed., 1998, Brown, Son and Ferguson, Glasgow, Scotland 11 Anonymous, Ammonium Nitrate Deposits Caused Unusual Fire at Laboratory, Fire Prevention, No 191, July/Aug 1986, 45-47

Prepared by Leith Higgins, Principal Scientific Officer, FESA Any comments 08 93239311 or Leith.Higgins@fesa.wa.gov.au Dec, 2008 by the Fire & Emergency Services Authority of Western Australia (FESA) This material is copyright and provided courtesy of FESA and published in the members only area of the AFAC Knowledge Web. The material is subject to the operation of the Copyright Act 1968 and its subsequent amendments. Material may be downloaded, displayed, printed and reproduced in unaltered form only for the sole use of AFAC members or partner organisations. This material may not be used for commercial purposes. Distribution of material from the members only area of the Knowledge Website to personnel outside of AFAC members and partner agencies is not permitted unless written authorisation is obtained from the content owner.

Ammonium nitrate can also be the cause of something unexpected. For example, there was a fire in 1988 at a major research laboratory in Switzerland, that started
20th January 2010 Page 3