Nitrogen trichloride

Nitrogen trichloride
Identifiers
CAS number 10025-85-1 Y
PubChem 61437
ChemSpider 55361 Y
ChEBI CHEBI:37382 Y
RTECS number QW974000
Jmol-3D images Image 1
Properties
Molar mass 120.365 g/mol
Appearance yellow oily liquid
Density 1.635 g/mL
Melting point

-40 °C, 233 K, -40 °F

Boiling point

71 °C, 344 K, 160 °F

Solubility in water Immiscible
slowly decomposes
Solubility soluble in benzene, chloroform, CCl4, CS2, PCl3
Structure
Crystal structure rhombohedral (below -40 °C)
Molecular shape trigonal pyramidal
Dipole moment 0.6 D
Thermochemistry
Std enthalpy of
formation
ΔfHo298
+232 kJ/mol
Standard molar
entropy
So298
 ? J.K−1.mol−1
Hazards
EU classification not listed
NFPA 704
0
2
4
OX
Autoignition
temperature
93 °C
Related compounds
Other anions Nitrogen trifluoride
Nitrogen tribromide
Nitrogen triiodide
Other cations Phosphorus trichloride
Arsenic trichloride
Related chloramines Chloramine
Dichloramine
Related compounds Nitrosyl chloride
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Nitrogen trichloride, also known as trichloramine, is the chemical compound with the formula NCl3. This yellow, oily, pungent-smelling liquid is most commonly encountered as a byproduct of chemical reactions between ammonia-derivatives and chlorine (for example, in swimming pools.

Contents

Preparation and structure

The compound is prepared by treatment of ammonium salts, such as ammonium nitrate with chlorine:

4 NH3 + 3 Cl2 → NCl3 + 3 NH4Cl

Intermediates in this conversion include chloramine and dichloramine, NH2Cl and NHCl2, respectively.

Like ammonia, NCl3 is a pyramidal molecule. The N-Cl distances are 1.76 Å, and the Cl-N-Cl angles are 107°.[1] The Pauling electronegativities are very similar for nitrogen (3.04) and chlorine (3.16).

Nitrogen trichloride can form in small amounts when public water supplies are disinfected with monochloramine, and between disinfecting chlorine and urea in urine from bathers). Nitrogen trichloride, trademarked as Agene, was used to artificially bleach and age flour.

Reactions

NCl3 is a highly reactive compound. The nitrogen in NCl3 is often considered to have the -3 oxidation state and the chlorine atoms are considered to be in the +1 oxidation state. Most of its reactivity is consistent with this description. It is hydrolyzed by hot water to release ammonia and hypochlorous acid.

NCl3 + 3 H2O → NH3 + 3 HOCl

Safety

Nitrogen trichloride can irritate mucous membranes - it is tear gas, but has never been used as such.[2].[3] The pure substance (rarely encountered) is a dangerous explosive, being sensitive to light, heat, even moderate shock, and organic compounds. Pierre Louis Dulong first prepared it in 1812, and lost two fingers and an eye in two separate explosions. An explosion from NCl3 blinded Sir Humphry Davy temporarily, inducing him to hire Michael Faraday as a co-worker.

In 2006, Belgian researchers reported a possible link between NCl3 and rising numbers of childhood asthma cases, in what they call the pool chlorine hypothesis, as an alternative to the hygiene hypothesis with a closer causal link.[4]

References

  1. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  2. ^ George Clifford White The handbook of chlorination and alternative disinfectants. 4th Edition, Wiley, 1999, ISBN 9780471292074, p. 322
  3. ^ National Institute for Occupational Safety and Health. (2008, August). NIOSH eNews, 6(4). Retrieved August 27, 2008, from http://www.cdc.gov/niosh/enews/enewsV6N4.html
  4. ^ Bernard A, Carbonnelle S, de Burbure C, Michel O, Nickmilder M (2006). "Chlorinated pool attendance, atopy, and the risk of asthma during childhood". Environmental Health Perspectives 114 (10): 1567–1573. doi:10.1289/ehp.8461. PMC 1626429. PMID 17035144. http://www.ehponline.org/members/2006/8461/8461.pdf. 

Further reading

External links