Nitrogen triiodide

Nitrogen triiodide
Nitrogen triiodide (structural formula)
Nitrogen triiodide
Nitrogen triiodide
Nitrogen triiodide
Nitrogen triiodide
Names
IUPAC names
Nitrogen triiodide[1]
Triiodoazane[1]
Triiodidonitrogen[1]
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 checkY
3D model (JSmol)
  • Interactive image
ChemSpider
  • 55511 checkY
PubChem CID
  • 61603
CompTox Dashboard (EPA)
  • DTXSID40893670 Edit this at Wikidata
InChI
  • InChI=1S/I3N/c1-4(2)3 checkY
    Key: FZIONDGWZAKCEX-UHFFFAOYSA-N checkY
  • InChI=1/I3N/c1-4(2)3
    Key: FZIONDGWZAKCEX-UHFFFAOYAL
  • 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,[2] such as diethyl ether
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Extremely explosive and unstable
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 4: Readily capable of detonation or explosive decomposition at normal temperatures and pressures. E.g. nitroglycerinSpecial hazards (white): no code
3
0
4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Chemical compound

Nitrogen triiodide is an inorganic compound with the formula NI3. 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 (C3v 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.

Infinite NI3·NH3 chain in the crystal structure

Decomposition and explosiveness

Detonation of 15g of nitrogen triiodide

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. ^ a b c per analogiam, see NF3 names, IUPAC Red Book 2005, p. 314
  2. ^ 4. Analytical techniques. acornusers.org
  3. ^ Tornieporth-Oetting, I.; Klapötke, T. (1990). "Nitrogen Triiodide". Angewandte Chemie International Edition. 29 (6): 677–679. doi:10.1002/anie.199006771.
  4. ^ a b Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  5. ^ Silberrad, O. (1905). "The Constitution of Nitrogen Triiodide". Journal of the Chemical Society, Transactions. 87: 55–66. doi:10.1039/CT9058700055.
  6. ^ 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.
  7. ^ Ford, L. A.; Grundmeier, E. W. (1993). Chemical Magic. Dover. p. 76. ISBN 0-486-67628-5.
  8. ^ 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. Bibcode:1958RSPSA.246..216B. doi:10.1098/rspa.1958.0123. S2CID 137728239.

External links

  • See the explosion
  • Nitrogen Tri-Iodide – explains why the compound is explosive
  • Nitrogen Tri-Iodide Detonation on Youtube
  • v
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Salts and covalent derivatives of the iodide ion
HI
+H
He
LiI BeI2 BI3
+BO3
CI4
+C
NI3
NH4I
+N
I2O4
I2O5
I4O9
IF
IF3
IF5
IF7
Ne
NaI MgI2 AlI
AlI3
SiI4 PI3
P2I4
+P
PI5
S2I2 ICl
ICl3
Ar
KI CaI2 ScI3 TiI2
TiI3
TiI4
VI2
VI3
CrI2
CrI3
MnI2 FeI2
FeI3
CoI2 NiI2
-Ni
CuI ZnI2 GaI
GaI3
GeI2
GeI4
+Ge
AsI3
As2I4
+As
Se IBr
IBr3
Kr
RbI
RbI3
SrI2 YI3 ZrI2
ZrI3
ZrI4
NbI4
NbI5
MoI2
MoI3
TcI3 RuI3 RhI3 PdI2 AgI CdI2 InI
InI3
SnI2
SnI4
SbI3
+Sb
TeI4
+Te
I
I
3
Xe
CsI
CsI3
BaI2   LuI3 HfI3
HfI4
TaI4
TaI5
WI2
WI3
WI4
ReI3
ReI
4
OsI
OsI2
OsI3
IrI3
IrI
4
PtI2
PtI4
AuI
AuI3
Hg2I2
HgI2
TlI
TlI3
PbI2 BiI3 PoI2
PoI4
AtI Rn
Fr RaI2   Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
LaI2
LaI3
CeI2
CeI3
PrI2
PrI3
NdI2
NdI3
PmI3 SmI2
SmI3
EuI2
EuI3
GdI2
GdI3
TbI3 DyI2
DyI
3
HoI3 ErI3 TmI2
TmI3
YbI2
YbI3
AcI3 ThI2
ThI3
ThI4
PaI4
PaI5
UI3
UI4
NpI3 PuI3 AmI2
AmI3
CmI3 BkI
3
CfI
2

CfI
3
EsI2
EsI3
Fm Md No
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Salts and covalent derivatives of the nitride ion
NH3
N2H4
+H
HN2−
H2N
He(N2)11
Li3N
LiN3
Be3N2
Be(N3)2
BN
-B
C2N2
β-C3N4
g-C3N4
CxNy
N2 NxOy
+O
N3F
N2F2
N2F4
NF3
+F
Ne
Na3N
NaN3
Mg3N2
Mg(N3)2
AlN Si3N4
-Si
PN
P3N5
-P
SxNy
SN
S2N2
S4N4
SN2H2
NCl3
ClN3
+Cl
Ar
K3N
KN3
Ca3N2
Ca(N3)2
ScN TiN
Ti3N4
VN CrN
Cr2N
MnxNy FexNy Co3N Ni3N Cu3N Zn3N2 GaN Ge3N4
-Ge
AsN
+As
Se4N4 Br3N
BrN3
+Br
Kr
RbN3 Sr3N2
Sr(N3)2
YN ZrN NbN β-Mo2N Tc Ru Rh PdN Ag3N Cd3N2 InN Sn SbN Te4N4? I3N
IN3
+I
Xe
CsN3 Ba3N2
Ba(N3)2
* LuN HfN
Hf3N4
TaN WN RexNy Os Ir Pt Au Hg3N2 Tl3N (PbNH) BiN Po At Rn
Fr Ra3N2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaN CeN PrN NdN PmN SmN EuN GdN TbN DyN HoN ErN TmN YbN
** Ac ThxNy PaN UxNy NpN PuN AmN CmN BkN Cf Es Fm Md No
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Nitrogen species
Hydrides
  • NH3
  • NH4+
  • NH2
  • N3−
  • NH2OH
  • N2H4
  • HN3
  • N3
  • NH5 (?)
Organic
Oxides
  • NO / (NO)2
  • N2O3
  • HNO2 / NO
    2
     / NO+
  • NO2 / (NO2)2
  • N2O5
  • HNO3 / NO
    3
     / NO+
    2
  • NO3
  • HNO / (HON)2 / N2O2−
    2
     / N2O
  • H2NNO2
  • HO2NO / ONOO
  • HO2NO2 / O2NOO
  • NO3−
    4
  • H4N2O4 / N2O2−
    3
Halides
  • NF
  • NF2
  • NF3
  • NF5 (?)
  • NCl3
  • NBr3
  • NI3
  • FN3
  • ClN3
  • BrN3
  • IN3
  • NH2F
  • N2F2
  • NH2Cl
  • NHF2
  • NHCl2
  • NHBr2
  • NHI2
Oxidation states
−3, −2, −1, 0, +1, +2, +3, +4, +5 (a strongly acidic oxide)