Hydrazinium azide

Last updated
Hydrazinium azide
Hydrazinium azide.svg
Names
IUPAC name
Hydrazinium azide
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/N3.H4N2/c1-3-2;1-2/h;1-2H2/q-1;/p+1
    Key: UZXHZRFWCCZBDW-UHFFFAOYSA-O
  • N[NH3+].[N-]=[N+]=[N-]
Properties [1]
H5N5
Molar mass 75.075 g·mol−1
AppearanceWhite solid
Melting point 75.4 °C (167.7 °F; 348.5 K)
Very soluble
Solubility in Methanol 6.1 g/100g (23 °C (73 °F; 296 K))
Solubility in Hydrazine 190 g/100g (23 °C (73 °F; 296 K))
Solubility in Ethanol 1.2 g/100g (23 °C (73 °F; 296 K))
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Hydrazinium azide or hydrazine azide is a chemical compound with formula H5N5 or [N2H+5][N−3]. It is a salt of the hydrazinium cation [N2H+5] and the azide anion N−3. It can be seen as a derivative of hydrazine N2H4 and hydrazoic acid HN3. It is an unstable solid.

Contents

When very pure, it is insensitive to ordinary levels of shock or impact and only decomposes slowly when heated, but less pure forms tend to explode when heated to a bit over 100 °C (212 °F) or when heated too rapidly. [1]

Structure

The solid undergoes structural phase transition to a different crystalline arrangement at a pressure of 13 GPa (130,000 atm). [2]

Preparation

Hydrazinium azide was first prepared by neutralizing hydrazoic acid with hydrazine hydrate. [1]

Chemistry

Hydrazinium azide decomposes explosively into hydrazine, ammonia, and nitrogen gas: [3]

12 N5H5 → 3 N2H4 + 16 NH3 + 19 N2

Crystallization with an equimolar amount hydrazine yields the solid hydrazinium azide hydrazinate, [N2H+5][N−3]·[N2H4], or N7H9, as monoclinic crystals. This compound is less hygroscopic and less volatile than pure hydrazinium azide. It decomposes explosively into nitrogen, hydrogen, and ammonia. [4]

At pressure of 40 GPa (390,000 atm), hydrazinium azide decomposes yielding a linear nitrogen allotrope N8 or N≡N+−N−−N=N−−N−+N≡N, that decomposes to ε−N2 below 25 GPa (250,000 atm). [2]

Reaction of hydrazinium azide with sulfuric acid gives quantitative yields of pure hydrazinediium sulfate and hydrazoic acid: [5]

[N2H+5][N−3] + H2SO4 → [N2H2+6][SO2−4] + HN3

See also

References

  1. 1 2 3 Fedoroff, Basil T.; Sheffield, Oliver E.; Clift, George D.; Reese, Earl F.; Aaronson, Henry A.; Dunkle, Cyrus G.; Walter, Hans; McLean, Dan C. (1960). "A - Azides - Hydrazine Azide". Encyclopedia of Explosives and Related Items (PDF) (Technical report). Vol. 1, A through Azoxy. Picatinny Arsenal, NJ: U.S. Army Research and Development Command TACOM - Ardec Warheads, Energetics and Combat Support Center. pp. A536-7. LCCN   61-61759. AD0257189, PATR2700.
  2. 1 2 Duwal, Sakun; Ryu, Young-Jay; Kim, Minseob; Yoo, Choong-Shik; Bang, Sora; Kim, Kyungtae; Hur, Nam Hwi (7 April 2018). "Transformation of hydrazinium azide to molecular N8 at 40 GPa". The Journal of Chemical Physics. 148 (13): 134310. Bibcode:2018JChPh.148m4310D. doi: 10.1063/1.5021976 . OSTI   1432864. PMID   29626901.
  3. ↑ G. B. Manelis (2003). Thermal decomposition and combustion of explosives and propellants. CRC Press. p. 235. ISBN   0-415-29984-5.
  4. ↑ Hammerl, Anton; Klapötke, Thomas M.; Piotrowski, Holger; Holl, Gerhard; Kaiser, Manfred (2001). "Synthesis and Characterization of Hydrazinium Azide Hydrazinate". Propellants, Explosives, Pyrotechnics. 26 (4): 161–164. doi:10.1002/1521-4087(200110)26:4<161::AID-PREP161>3.0.CO;2-O.
  5. ↑ Klapötke, T.; Peter S. White; Inis C. Tornieporth-Oetting (1996). "Reaction of hydrazinium azide with sulfuric acid: the X-ray structure of [N
    2    H
    6    ][SO
    4    ]    ". Polyhedron. 15 (15): 2579–2582. doi:10.1016/0277-5387(95)00527-7.
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