Nitrogen triiodide

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Nitrogen triiodide
Nitrogen-iodide-2D.png
Nitrogen triiodide Nitrogen-triiodide-3D-balls.png
Nitrogen triiodide
Nitrogen triiodide Nitrogen-triiodide-3D-vdW.png
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
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/I3N/c1-4(2)3 Yes check.svgY
    Key: FZIONDGWZAKCEX-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/I3N/c1-4(2)3
    Key: FZIONDGWZAKCEX-UHFFFAOYAL
  • IN(I)I
Properties
NI3
Molar mass 394.719 g/mol
Appearancedark solid
Boiling point sublimes at −20 °C
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.svgHealth 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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Nitrogen triiodide is an inorganic compound with the formula N I 3. 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.

Contents

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.

NH3*NI3-chain-from-xtal-3D-bs-20.png

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]

Related Research Articles

<span class="mw-page-title-main">Explosive</span> Substance that can explode

An explosive is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An explosive charge is a measured quantity of explosive material, which may either be composed solely of one ingredient or be a mixture containing at least two substances.

<span class="mw-page-title-main">Iodine</span> Chemical element with atomic number 53 (I)

Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at 114 °C (237 °F), and boils to a violet gas at 184 °C (363 °F). The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek Ιώδης, meaning 'violet'.

<span class="mw-page-title-main">Nitrogen</span> Chemical element with atomic number 7 (N)

Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colourless and odourless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant chemical species in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.

<span class="mw-page-title-main">Ammonium nitrate</span> Chemical compound with formula NH4NO3

Ammonium nitrate is a chemical compound with the formula NH4NO3. It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, although it does not form hydrates. It is predominantly used in agriculture as a high-nitrogen fertilizer.

<span class="mw-page-title-main">Lewis acids and bases</span> Chemical bond theory

A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane [(CH3)3B] is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis.

In chemistry, azide is a linear, polyatomic anion with the formula N−3 and structure N=N+=N. It is the conjugate base of hydrazoic acid HN3. Organic azides are organic compounds with the formula RN3, containing the azide functional group. The dominant application of azides is as a propellant in air bags.

<span class="mw-page-title-main">Nitrogen trichloride</span> Chemical compound

Nitrogen trichloride, also known as trichloramine, is the chemical compound with the formula NCl3. This yellow, oily, and explosive liquid is most commonly encountered as a product of chemical reactions between ammonia-derivatives and chlorine. Alongside monochloramine and dichloramine, trichloramine is responsible for the distinctive 'chlorine smell' associated with swimming pools, where the compound is readily formed as a product from hypochlorous acid reacting with ammonia and other nitrogenous substances in the water, such as urea from urine.

<span class="mw-page-title-main">Silver fulminate</span> High explosive used in bang snaps

Silver fulminate (AgCNO) is the highly explosive silver salt of fulminic acid.

<span class="mw-page-title-main">Hydrazoic acid</span> Unstable and toxic chemical compound

Hydrazoic acid, also known as hydrogen azide, azic acid or azoimide, is a compound with the chemical formula HN3. It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. The oxidation state of the nitrogen atoms in hydrazoic acid is fractional and is -1/3. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

<span class="mw-page-title-main">Phosphorus triiodide</span> Chemical compound

Phosphorus triiodide (PI3) is an inorganic compound with the formula PI3. A red solid, it is too unstable to be stored for long periods of time; it is, nevertheless, commercially available. It is widely used in organic chemistry for converting alcohols to alkyl iodides. It is also a powerful reducing agent.

Shock sensitivity is a comparative measure of the sensitivity to sudden compression of an explosive chemical compound. Determination of the shock sensitivity of a material intended for practical use is one important aspect of safety testing of explosives. A variety of tests and indices are in use, of which one of the more common is the Rotter Impact Test with results expressed as FoI At least four other impact tests are in common use, while various "gap tests" are used to measure sensitivity to blast shock.

<span class="mw-page-title-main">Triiodide</span> Ion

In chemistry, triiodide usually refers to the triiodide ion, I
3
. This anion, one of the polyhalogen ions, is composed of three iodine atoms. It is formed by combining aqueous solutions of iodide salts and iodine. Some salts of the anion have been isolated, including thallium(I) triiodide (Tl+[I3]) and ammonium triiodide ([NH4]+[I3]). Triiodide is observed to be a red colour in solution.

<span class="mw-page-title-main">Tetrasulfur tetranitride</span> Chemical compound

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This vivid orange, opaque, crystalline explosive is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.

<span class="mw-page-title-main">Contact explosive</span> Substance which explodes when exposed to small amounts of energy

A contact explosive is a chemical substance that explodes violently when it is exposed to a relatively small amount of energy. Though different contact explosives have varying amounts of energy sensitivity, they are all much more sensitive relative to other kinds of explosives. Contact explosives are a part of a group of explosives called primary explosives, which are also very sensitive to stimuli but not to the degree of contact explosives. The extreme sensitivity of contact explosives is due to either chemical composition, bond type, or structure.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

<span class="mw-page-title-main">Ammonium permanganate</span> Chemical compound

Ammonium permanganate is the chemical compound NH4MnO4, or NH3·HMnO4. It is a water soluble, violet-brown or dark purple salt.

Iodine monofluoride is an interhalogen compound of iodine and fluorine with formula IF. It is a chocolate-brown solid that decomposes at 0 °C, disproportionating to elemental iodine and iodine pentafluoride:

<span class="mw-page-title-main">Ammonium iodate</span> Chemical compound

Ammonium iodate is an inorganic salt which is sparingly soluble in cold, and moderately soluble in hot water, like all iodate salts, it is a strong oxidizer.

Europium(III) iodide is an inorganic compound containing europium and iodine with the chemical formula EuI3.

References

  1. 1 2 3 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. 1 2 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.