Hydrazoic acid
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| Names | |
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| IUPAC name
Hydrogen azide
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| Other names
Hydrogen azide
Azoimide Azic acid | |
| Identifiers | |
3D model (
JSmol ) |
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| ChEBI | |
| ChEMBL | |
| ChemSpider | |
ECHA InfoCard
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100.029.059 |
| EC Number |
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| 773 | |
PubChem CID
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| UNII | |
CompTox Dashboard (EPA)
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| Properties | |
| HN3 | |
| Molar mass | 43.029 g·mol−1 |
| Appearance | colorless, highly volatile liquid |
| Density | 1.09 g/cm3 |
| Melting point | −80 °C (−112 °F; 193 K) |
| Boiling point | 37 °C (99 °F; 310 K) |
| highly soluble | |
| Solubility | soluble in alkali, alcohol, ether |
| Acidity (pKa) | 4.6 [1] |
Conjugate base
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Azide |
| Structure | |
| approximately linear | |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
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Highly toxic, explosive, reactive |
| GHS labelling: | |
  
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| Danger | |
| H200, H319, H335, H370 | |
| P201, P202, P260, P261, P264, P270, P271, P280, P281, P304+P340, P305+P351+P338, P307+P311, P312, P321, P337+P313, P372, P373, P380, P401, P403+P233, P405, P501 | |
| NFPA 704 (fire diamond) | |
| Related compounds | |
Other cations
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Sodium azide Lithium azide Potassium azide |
| Ammonia Hydrazine | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hydrazoic acid, also known as hydrogen azide, azic acid or azoimide,
Hydrazoic acid, like its fellow mineral acids, is soluble in water. Undiluted hydrazoic acid is dangerously explosive[5] with a standard enthalpy of formation ΔfHo (l, 298K) = +264 kJ/mol.[6] When dilute, the gas and aqueous solutions (<10%) can be safely prepared but should be used immediately; because of its low boiling point, hydrazoic acid is enriched upon evaporation and condensation such that dilute solutions incapable of explosion can form droplets in the headspace of the container or reactor that are capable of explosion.[7][8]
Production
The acid is usually formed by acidification of an azide salt like sodium azide. Normally solutions of sodium azide in water contain trace quantities of hydrazoic acid in equilibrium with the azide salt, but introduction of a stronger acid can convert the primary species in solution to hydrazoic acid. The pure acid may be subsequently obtained by fractional distillation as an extremely explosive colorless liquid with an unpleasant smell.[2]
- NaN3 + HCl → HN3 + NaCl
Its aqueous solution can also be prepared by treatment of barium azide solution with dilute sulfuric acid, filtering the insoluble barium sulfate.[9]
It was originally prepared by the reaction of aqueous hydrazine with nitrous acid:
- N2H4 + HNO2 → HN3 + 2 H2O
With the hydrazinium cation [N2H5]+ this reaction is written as:
- [N2H5]+ + HNO2 → HN3 + H2O + [H3O]+
Other oxidizing agents, such as
Destruction prior to disposal
Hydrazoic acid reacts with nitrous acid:
- HN3 + HNO2 → N2O + N2 + H2O
This reaction is unusual in that it involves compounds with nitrogen in four different oxidation states.[11]
Reactions
In its properties hydrazoic acid shows some analogy to the halogen acids, since it forms poorly soluble (in water) lead, silver and mercury(I) salts. The metallic salts all crystallize in the anhydrous form and decompose on heating, leaving a residue of the pure metal.
Hydrazoic acid may react with carbonyl derivatives, including aldehydes, ketones, and carboxylic acids, to give an amine or amide, with expulsion of nitrogen. This is called Schmidt reaction or Schmidt rearrangement.
Dissolution in the strongest acids produces explosive salts containing the aminodiazonium ion [H2N=N=N]+ ⇌ [H2N−N≡N]+, for example:[12]
- HN=N=N + H[SbCl6] → [H2N=N=N]+[SbCl6]−
The ion [H2N=N=N]+ is
The decomposition of hydrazoic acid, triggered by shock, friction, spark, etc. produces nitrogen and hydrogen:
- 2 HN3 → H2 + 3 N2
Hydrazoic acid undergoes unimolecular decomposition at sufficient energy:
- HN3 → NH + N2
The lowest energy pathway produces NH in the triplet state, making it a spin-forbidden reaction. This is one of the few reactions whose rate has been determined for specific amounts of vibrational energy in the ground electronic state, by laser photodissociation studies.[13] In addition, these unimolecular rates have been analyzed theoretically, and the experimental and calculated rates are in reasonable agreement.[14]
Toxicity
Hydrazoic acid is volatile and highly toxic. It has a pungent smell and its vapor can cause violent headaches. The compound acts as a non-cumulative poison.
Applications
2-Furonitrile, a pharmaceutical intermediate and potential artificial sweetening agent has been prepared in good yield by treating furfural with a mixture of hydrazoic acid (HN3) and perchloric acid (HClO4) in the presence of magnesium perchlorate in the benzene solution at 35 °C.[15][16]
The
References
- ISBN 0-07-049439-8
- ^ a b c Chisholm, Hugh, ed. (1911). . Encyclopædia Britannica. Vol. 3 (11th ed.). Cambridge University Press. pp. 82–83. This also contains a detailed description of the contemporaneous production process.
- ^ Dictionary of Inorganic and Organometallic Compounds. Chapman & Hall.
- .
- S2CID 102029987.
- ^ ISBN 978-0-13-175553-6.
- ^ Gonzalez-Bobes, F. et al Org. Process Res. Dev. 2012, 16, 2051-2057.
- ^ Treitler, D. S. et al Org. Process Res. Dev. 2017, 21, 460-467.
- ^ L . F. Audrieth, C. F. Gibbs Hydrogen Azide in Aqueous and Ethereal Solution" Inorganic Syntheses 1939, vol. 1, pp. 71-79.
- ISBN 978-0-08-037941-8.
- ^ Greenwood, pp. 461–464.
- ^ ISBN 978-0-12-352651-9.
- doi:10.1063/1.457924.
- PMID 18681642.
- ^ P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine". Khimiya Geterotsiklicheskikh Soedinenii. 2: 181–186.
- S2CID 98593006.
External links
Media related to Hydrogen azide at Wikimedia Commons- OSHA: Hydrazoic Acid Archived 2008-04-04 at the Wayback Machine
