Nitrogen Triiodide

The well-known explosive crystals

Simon Cotton
Uppingham School, Rutland, UK
Nitrogen triiodide, NI3

Molecule of the Month December 2001

Also available: JSmol versions.

Sounds like another boring covalent molecule

This one's explosive! When dry solid nitrogen triiodide is touched, even with a feather, it decomposes rather violently. Click on the
images below to see an animation.

2 NI3 (s) N2 (g) + 3 I2 (s)

Before... ...After

Very impressive! The purple smoke is iodine vapour, I suppose?

Yes. In the animation, the shockwave from the first detonation sets off the second sample of NI3.

Why is it so explosive?
The process 2 NI3 (s) N2 (g) + 3 I2 (s) is exothermic, so that N2 (g) + 3 I2 (s) 2 NI3 (s) is endothermic. Endothermic
compounds tend to be unstable.

Is that all?
Not at all, things are more complicated than they seem. Traditionally, nitrogen triiodide is made by reacting iodine with aqueous
ammonia solution. That does not produce NI3, an ammonia complex is obtained instead. This is either [NI3.NH3] or [NI3.(NH3)3], and
the ammonia cannot be removed from this.

So can pure NI3 be made?

This wasn't achieved until 1990, when it was found that boron nitride reacted with iodine monofluoride in CFCl3 at -30°C.

BN + 3 IF BF3 + NI3

What is pure NI3 like?

It's a dark red solid that can be sublimed in a vacuum at -20°C. It decomposes at 0°C, sometimes explosively.

Can you make other nitrogen trihalides?

Yes, certainly, thanks to some brave and intrepid chemists. NCl3 was the first of the family to be made in 1811, by Pierre L.Dulong,
who later became Professor of Chemistry at the Ecole Polytechnique in Paris; he lost 3 fingers and an eye in studying it. He made it by
the reaction of chlorine with slightly acidic NH4Cl. The main route used commercially today is the electrolysis of slightly acidic
ammonium chloride; the NCl3 is removed as fast it is formed using an air current. This air/NCl3 mixture is much more stable than pure
NCl3 and is commercially important. It is also formed in swimming pools when the chlorine gas used to disinfect the water reacts with
nitrogen compounds found in urine, and can be a health risk to people like lifeguards who work continuously around the water. NCl3
can be formed when chlorine reacts with nitrogen compounds in wastewater treatment plants. The particular danger associated with
the formation of NCl3 under these conditions is that a combination of its sensitive nature and low solubility in water leads to explosive
droplets of NCl3.

Stable NF3 was first made in 1928 by Otto Ruff, a German chemist (d.1939) who probably made more fluorides than anyone else, by
electrolysis of a molten mixture of ammonium fluoride and hydrogen fluoride. Another route uses the reaction of ammonia with
fluorine/nitrogen mixtures over a copper catalyst.

4NH3 + 3 F2 NF3 + 3 NH4F

NBr3 was originally synthesised in 1975 by the reaction of bis(trimethylsilyl)bromamine with ClBr at -78°C.

(Me3Si)2NBr + 2 BrCl NBr3 + 2 Me3SiCl

What are they like?

NF3 is pretty unreactive at room temperature; it is not affected by water and only reacts with most metals on heating. NCl3 is much
more reactive; it is light-sensitive and, like all the other halides, apart from NF3, explosive. All these compounds are volatile, as
expected for small covalent molecules.

Why is NF3 stable but the others are unstable?

For all these compounds, it is possible to work out ΔHf for the formation of NX3 in the gas phase, using bond energies.

N2 (g) + 3 X2 (g) 2 NX3 (g)

The process is not especially favourable owing to the difficulty in breaking the very strong N-N triple bond (E(N-N) = 945 kJ mol-1).
Using values for the F-F and N-F bond energies of 159 and 278 kJ mol-1, respectively, ΔHf ) = - 123 kJ mol-1 (per mole of NF3);
similarly, for ammonia, using H-H and N-H bond energies of 436 and 390 kJ mol-1, respectively, ΔHf = - 43 kJ mol-1 (per mole of
NH3). In contrast, using I-I and N-I bond energies of 151 and 169 kJ mol-1, respectively, ΔHf per mole of NI3 = + 192 kJ mol-1.

One factor making NF3 more stable than the other NX3 is the very low F-F bond energy (159 kJ mol-1).
This has been ascribed to repulsions between lone pairs on the two rather proximate fluorine atoms.
Additionally, the N-F bond is also particularly strong, as would be expected for a linkage between two
elements in the first short period. The other NX3 molecules may be less stable than NF3 owing to
congestion round the small central nitrogen atom leading to non-bonded repulsive interactions between
the halogens. This is particularly bad for large iodine atoms, as can be seen in the space-fill image of NI3,
right.

What is their structure?

In all these compounds, the nitrogen atom has a complete "octet", with four outer-shell electron pairs; one of these is a non-bonding
("lone") pair. These arrange themselves as far apart as possible around the nitrogen atom in a roughly tetrahedral disposition, to
minimise repulsions between the negative charge clouds.

However, because repulsions involving lone pairs are stronger than those involving just bond pairs, the X-N-X angles are a little under
the regular tetrahedral angle of 109½°; thus the value for ammonia, NH3, is 107.5°. Because fluorine is much more electronegative
than hydrogen, the bond pairs of electrons are attracted away from nitrogen, so that in NF3 the bond angle is actually 102.3°. In
contrast, the corresponding value for NCl3 is 107.1°, although on electronegativity grounds it would be expected to be intermediate
between the values for NF3 and NH3. This may possibly be due to non-bonded Cl...Cl repulsions.

The molecules themselves have a trigonal (triangular) pyramid shape. They are, of course, polar. NF3 has a small dipole moment
(0.234D) in comparison with NH3 (1.42D); an explanation for this is that the moment due to the nitrogen atom and its lone pair is in
opposition to the moment associated with the three polar N-F bonds in NF3. NCl3 also has a small dipole moment (0.6D).

They sound very exotic- do they actually have any uses?

NCl3 is used as a dilute mixture in air to bleach and sterilise flour and as a fungicide for citrus fruits and melons. The semiconductor
industry uses NF3 as an etchant of thin films, also for cleaning up chemical vapour deposition chambers, both uses depending on the
use of a plasma to produce fluorine from NF3. It is also used as an oxidizer of high energy fuels, for the preparation of
tetrafluorohydrazine (another fuel), and for the fluorination of fluorocarbon olefins, whilst it has been studies as a high-energy oxidiser
for HF-DF chemical lasers.

A comparison of NX3
 NF3 NCl3 NBr3 NI3
First synthesised 1928 1811 1975 1990 (ammonia adduct 1813)
Description (at RT) Colourless gas Pale yellow oil Deep red solid Red-black crystals
m.p. (°C) -208.5 -40 - -
b.p. (°C) -129 71 - -
< X-N-X (°) 102.3 107.1 - -
N-X (pm) 137 175.9 - -
N-X bond energy (kJ mol-1) 278 188 169 -
Dipole moment (D) 0.234 0.6 - -
ΔHf (kJ mol-1) -114 232 220 (est) 159 (est)

Bibliography

N.N. Greenwood and A. Earnshaw, Chemistry of the Elements, Butterworth Heinemann, 2nd edition, 1997, 438-441
F.A. Cotton, C. Murillo, G. Wilkinson, M. Bochman and R. Grimes, Advanced Inorganic Chemistry, John Wiley, 6th edition 1999,
335-338
J.E. Macintyre (ed), Dictionary of Inorganic Compounds, Chapman and Hall, London, 1992, entries IC-001954; IC-016907; IC-
018291; IC-020275
H.H. Sisler, in Encyclopedia of Inorganic Chemistry, R.B. King ed, Wiley, 1994, Vol.5pp 2545-2551.
J. Jander, Adv. Inorg.Chem., 1976, 19, 1 (review of NX3, not X=F)
H.J. Emeléus, J.M. Shreeve and R.D. Verma, Adv. Inorg. Chem., 1989, 33, 139 (review of NF3)
Synthesis of NI3 : I. Tornieporth-Oetting and T. Klapötke, Angew. Chem. Int. Ed. Engl., 1990, 29, 677
Synthesis of NBr3: J. Jander, J. Knackmuss and K-U. Thiedemann, Z. Naturforsch. Teil B, 1975, 30, 464
Enthalpy of formation of NI3 : R.H. Davies, A. Finch and P.N. Gates, J.Chem. Soc .Chem. Comm., 1989, 1461.
NCl3 structure: H. Hartl, J. Schöner, J. Jander and H. Schulz, Z. Anorg. Allgem. Chem., 1975, 413, 61
NI3 adducts structure: J. Jander, L. Bayersdorfer and K. Höhne, Z. Anorg. Allgem. Chem., 1968, 357, 225.
NCl3: http://inst.augie.edu/~djpaulso/indexA.html (rev)
Shape: R.J. Gillespie and I Hargittai, The VSEPR Model of Molecular Geometry, Allyn and Bacon, Boston, 1991, p. 81.
Stability: W.E. Dasent, Non-existent Compounds, Marcel Dekker, New York, 1965, pp 30-31
Uses and properties:
http://www.semi.org/web/wsemi.nsf/364c709e8ffa8f9a882565de0080afe5/a666d06d06cb01ce8825696000815ef4!OpenDocument
(NF3)
http://www.unfccc.int/program/wam/wamsub024.html (NF3)
http://www.c-f-c.com/gaslink/pure/nitrogen-trifluoride.htm (NF3)
C. Shang, W-L. Gong and E.R. Blatchley, Environ.Sci.Technol., 2000, 34, 1721 (NCl3)
http://www.chem.purdue.edu/margerum/breakcl2.html (NCl3)
http://www.amarillonet.com/stories/010497/010497.html (NCl3)

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