Hydrazoic acid

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Hydrazoic acid
Structure, bonding and dimensions of the hydrogen azide molecule
Hydrazoic acid
Hydrazoic acid
Identifiers
CAS number 7782-79-8 YesY
PubChem 24530
ChemSpider 22937 YesY
ChEBI CHEBI:29449 YesY
ChEMBL CHEMBL186537 YesY
Jmol-3D images Image 1
Properties
Molecular formula HN3
Molar mass 43.03 g/mol
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)
Solubility in water highly soluble
Solubility soluble in alkali, alcohol, ether
Acidity (pKa) 4.6 [1]
Structure
Molecular shape approximately linear
Hazards
EU Index Not listed
R-phrases R3, R27/28
S-phrases S33, S36/37, S38
Main hazards Highly toxic, explosive, reactive
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 4: Very short exposure could cause death or major residual injury. E.g., VX gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazards (white): no codeNFPA 704 four-colored diamond
Related compounds
Other cations Sodium azide
Related nitrogen hydrides Ammonia
Hydrazine
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Hydrazoic acid, also known as hydrogen azide or azoimide,[2] is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, having chemical formula HN3.[3] It was first isolated in 1890 by Theodor Curtius.[4] The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

Hydrazoic acid is soluble in water. Undiluted hydrazoic acid is dangerously explosive with a standard enthalpy of formation ΔfHo (l, 298K) = +264 kJmol−1).[5] When dilute, the gas and aqueous solutions (<10%) can be safely handled.

Production[edit]

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.

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.[6]

It was originally prepared by the reaction of aqueous hydrazine with nitrous acid.

N2H5+ + HNO2 → HN3 + H+ + 2 H2O

Other oxidizing agents, such as hydrogen peroxide or nitric acid, can also be used.[7]

Reactions[edit]

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. It is a weak acid (pKa = 4.75.[5]) Its heavy metal salts are explosive and readily interact with the alkyl iodides. Azides of heavier alkali metals (excluding lithium) or alkaline earth metals are not explosive, but decompose in a more controlled way upon heating, releasing spectroscopically-pure N
2
gas.[8] Solutions of hydrazoic acid dissolve many metals (e.g. zinc, iron) with liberation of hydrogen and formation of salts, which are called azides, formerly also called azoimides or hydrazoates).

Dissolution in the strongest acids produces explosive salts containing the H
2
N=N=N+
ion, for example:[8]

HN=N=N + HSbCl
6
[H
2
N=N=N]+
[SbCl
6
]

The ion H
2
N=N=N+
is isoelectronic to diazomethane.

The decomposition of hydrazoic acid, triggered by shock, friction, spark, etc. goes as follows:

2HN
3
H
2
+ 3N
2

Toxicity[edit]

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[edit]

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 in the presence of magnesium perchlorate in the benzene solution at 35 °C.[9][10]

The all gas-phase iodine laser (AGIL) mixes gaseous hydrazoic acid with chlorine to produce excited nitrogen chloride, which is then used to cause iodine to lase; this avoids the liquid chemistry requirements of COIL lasers.

References[edit]

  1. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  2. ^  Chisholm, Hugh, ed. (1911). "Azoimide". Encyclopædia Britannica 3 (11th ed.). Cambridge University Press. 
  3. ^ Dictionary of Inorganic and Organometallic Compounds. Chapman & Hall. 
  4. ^ Curtius, Theodor (1890). Berichte 23: 3023. 
  5. ^ a b Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 15: The group 15 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 449. ISBN 978-0-13-175553-6. 
  6. ^ L . F. Audrieth, C. F. Gibbs Hydrogen Azide in Aqueous and Ethereal Solution" Inorganic Syntheses 1939, vol. 1, pp. 71-79.
  7. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 432. ISBN 0080379419. 
  8. ^ a b Egon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). "The Nitrogen Group". Inorganic chemistry. Academic Press. p. 625. ISBN 0-12-352651-5. 
  9. ^ P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine". Khimiya Geterotsiklicheskikh Soedinenii 2: 181–186. 
  10. ^ B. Bandgar; Makone, S. (2006). "Organic reactions in water. Transformation of aldehydes to nitriles using NBS under mild conditions". Synthetic Communications 36 (10): 1347–1352. doi:10.1080/00397910500522009. 

External links[edit]