Chemistry:Nitrogen triiodide

Nitrogen triiodide
Names
	IUPAC names Nitrogen triiodide; Triiodoazane; Triiodidonitrogen
	Other names Nitrogen iodide; Ammonia triiodide; Touch Powder; Triiodine nitride; Triiodine mononitride; Triiodamine[citation needed]; Triiodoamine[citation needed]; Iodine nitride
Identifiers
CAS Number	13444-85-4 ;
3D model (JSmol)	Interactive image;
ChemSpider	55511 ;
PubChem CID	61603;
	InChI InChI=1S/I3N/c1-4(2)3 Key: FZIONDGWZAKCEX-UHFFFAOYSA-N ; InChI=1/I3N/c1-4(2)3 Key: FZIONDGWZAKCEX-UHFFFAOYAL;
	SMILES IN(I)I;
Properties
Chemical formula	NI3
Molar mass	394.719 g/mol
Appearance	dark solid
Boiling point	sublimes at −20 °C
Solubility in water	Insoluble
Solubility	organic solvents, such as diethyl ether
Hazards
Main hazards	Extremely explosive and unstable
NFPA 704 (fire diamond)	0 3 4
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	verify (what is ?)
	Infobox references

Nitrogen triiodide is an inorganic compound with the formula N I₃. It is an extremely sensitive contact explosive: small quantities explode with a loud, sharp snap when touched even lightly, releasing a purple cloud of iodine vapor; it can even be detonated by alpha radiation. NI₃ has a complex structural chemistry that is difficult to study because of the instability of the derivatives. Although nitrogen is more electronegative than iodine, the compound was so named due to its analogy to the compound nitrogen trichloride.^{[citation needed]}

Structure of NI₃ and its derivatives

Nitrogen triiodide was first characterized by Raman spectroscopy in 1990 when it was prepared by an ammonia-free route. Boron nitride reacts with iodine monofluoride in trichlorofluoromethane at −30 °C to produce pure NI₃ in low yield:^[3]

BN + 3 IF → NI₃ + BF₃

NI₃ is pyramidal (C_3v molecular symmetry), as are the other nitrogen trihalides and ammonia.^[4]

The material that is usually called "nitrogen triiodide" is prepared by the reaction of iodine with ammonia. When this reaction is conducted at low temperatures in anhydrous ammonia, the initial product is NI₃ · (NH₃)₅, but this material loses some ammonia upon warming to give the 1:1 adduct NI₃ · NH₃. This adduct was first reported by Bernard Courtois in 1812, and its formula was finally determined in 1905 by Oswald Silberrad.^[5] Its solid state structure consists of chains of -NI₂-I-NI₂-I-NI₂-I-.^[6] Ammonia molecules are situated between the chains. When kept cold in the dark and damp with ammonia, NI₃ · NH₃ is stable.

Decomposition and explosiveness

File:Detonating Nitrogen triiodide.webm

The instability of NI₃ and NI₃ · NH₃ can be attributed to the large steric strain caused by the three large iodine atoms being held in proximity to each other around the relatively tiny nitrogen atom. This results in a very low activation energy for its decomposition, a reaction made even more favorable due to the great stability of N₂. Nitrogen triiodide has no practical commercial value due to its extreme shock sensitivity, making it impossible to store, transport, and utilize for controlled explosions. Whereas pure nitroglycerin is powerful and also greatly shock-sensitive (although not nearly as much so as nitrogen triiodide, which can be set off with the touch of a feather), it was only due to phlegmatizers that nitroglycerin's shock sensitivity was reduced and it became safer to handle and transport in the form of dynamite.

The decomposition of NI₃ proceeds as follows to give nitrogen gas and iodine:

2 NI₃ (s) → N₂ (g) + 3 I₂ (g) (−290 kJ/mol)

However, the dry material is a contact explosive, decomposing approximately as follows:^[4]

8 NI₃ · NH₃ → 5 N₂ + 6 NH₄I + 9 I₂

Consistent with this equation, these explosions leave orange-to-purple stains of iodine, which can be removed with sodium thiosulfate solution. An alternate method of stain removal is to simply allow the iodine time to sublime. Small amounts of nitrogen triiodide are sometimes synthesized as a demonstration to high school chemistry students or as an act of "chemical magic."^[7] To highlight the sensitivity of the compound, it is usually detonated by touching it with a feather, but even the slightest air current, laser light, or other movement can cause detonation. Nitrogen triiodide is also notable for being the only known chemical explosive that detonates when exposed to alpha particles and nuclear fission products.^[8]

References

↑ ^1.0 ^1.1 ^1.2 per analogiam, see NF₃ names, IUPAC Red Book 2005, p. 314
↑ 4. Analytical techniques. acornusers.org
↑ Tornieporth-Oetting, I.; Klapötke, T. (1990). "Nitrogen Triiodide". Angewandte Chemie International Edition 29 (6): 677–679. doi:10.1002/anie.199006771.
↑ ^4.0 ^4.1 Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
↑ Silberrad, O. (1905). "The Constitution of Nitrogen Triiodide". Journal of the Chemical Society, Transactions 87: 55–66. doi:10.1039/CT9058700055. https://zenodo.org/record/1429707.
↑ Hart, H.; Bärnighausen, H.; Jander, J. (1968). "Die Kristallstruktur von Stickstofftrijodid‐1‐Ammoniak NJ₃ · NH₃". Z. Anorg. Allg. Chem. 357 (4–6): 225–237. doi:10.1002/zaac.19683570410.
↑ Ford, L. A.; Grundmeier, E. W. (1993). Chemical Magic. Dover. p. 76. ISBN 0-486-67628-5. https://archive.org/details/chemicalmagic00ford_0/page/76.
↑ Bowden, F. P. (1958). "Initiation of Explosion by Neutrons, α-Particles, and Fission Products". Proceedings of the Royal Society of London A 246 (1245): 216–219. doi:10.1098/rspa.1958.0123. Bibcode: 1958RSPSA.246..216B.

External links

HI																	He
LiI	BeI₂											BI₃	CI₄	NI₃	I₂O₄, I₂O₅, I₄O₉	IF, IF₃, IF₅, IF₇	Ne
NaI	MgI₂											AlI₃	SiI₄	PI₃, P₂I₄	S	ICl, ICl₃	Ar
KI	CaI₂	Sc	TiI₄	VI₃	CrI₃	MnI₂	FeI₂	CoI₂	NiI₂	CuI	ZnI₂	Ga₂I₆	GeI₂, GeI₄	AsI₃	Se	IBr	Kr
RbI	SrI₂	YI₃	ZrI₄	NbI₅	Mo	Tc	Ru	Rh	Pd	AgI	CdI₂	InI₃	SnI₄, SnI₂	SbI₃	TeI₄	I	Xe
CsI	BaI₂		HfI₄	TaI₅	W	Re	Os	Ir	Pt	AuI	Hg₂I₂, HgI₂	TlI	PbI₂	BiI₃	Po	AtI	Rn
Fr	RaI₂		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Nh	Fl	Mc	Lv	Ts	Og
		↓
		La	Ce	Pr	Nd	Pm	SmI₂	Eu	Gd	TbI₃	Dy	Ho	Er	Tm	Yb	Lu
		Ac	ThI₄	Pa	UI₃, UI₄	Np	Pu	Am	Cm	Bk	Cf	EsI₃	Fm	Md	No	Lr