Hydrazoic acid

Hydrazoic acid
Names
	IUPAC name Hydrogen azide
	Other names Hydrogen azide; Azoimide; Azic acid
Identifiers
CAS Number	7782-79-8;
3D model (JSmol)	Interactive image; Interactive image;
ChEBI	CHEBI:29449;
ChEMBL	ChEMBL186537;
ChemSpider	22937;
ECHA InfoCard	100.029.059
EC Number	231-965-8;
Gmelin Reference	773
PubChemCID	24530;
UNII	6P5C4D5D7I;
CompTox Dashboard(EPA)	DTXSID20884425;
	InChI InChI=1S/HN3/c1-3-2/h1H Key: JUINSXZKUKVTMD-UHFFFAOYSA-N; InChI=1/HN3/c1-3-2/h1H Key: JUINSXZKUKVTMD-UHFFFAOYAO;
	SMILES [N-]=[N+]=N; N#[N+][N-H];
Properties
Chemical formula	HN3
Molar mass	43.029g·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)
Solubility in water	highly soluble
Solubility	soluble inalkali,alcohol,ether
Acidity(pKa)	4.6
Conjugate base	Azide
Structure
Molecular shape	approximately linear
Hazards
	Occupational safety and health(OHS/OSH):
Main hazards	Highly toxic, explosive, reactive
	GHSlabelling:
Pictograms
Signal word	Danger
Hazard statements	H200,H319,H335,H370
Precautionary statements	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)	4 0 3
Related compounds
Othercations	Sodium azide; Lithium azide; Potassium azide
Relatednitrogenhydrides	Ammonia; Hydrazine
	Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa). verify(what is?) Infobox references

Hydrazoic acid,also known ashydrogen azide,azic acidorazoimide,^[2]is a compound with the chemical formulaHN₃.^[3]It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound ofnitrogenandhydrogen,and is therefore apnictogen hydride.Theoxidation stateof the nitrogen atoms in hydrazoic acid is fractional and is -1/3.^{[citation needed]}It was first isolated in 1890 byTheodor Curtius.^[4]The acid has few applications, but itsconjugate base,theazideion, is useful in specialized processes.

Hydrazoic acid, like its fellowmineral acids,is soluble in water. Undiluted hydrazoic acid is dangerously explosive^[5]with astandard enthalpy of formationΔ_fH^o(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 likesodium 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 byfractional distillationas an extremely explosive colorless liquid with an unpleasant smell.^[2]

NaN₃+ HCl → HN₃+ NaCl

Its aqueous solution can also be prepared by treatment ofbarium azidesolution with dilutesulfuric acid,filtering the insolublebarium sulfate.^[9]

It was originally prepared by the reaction of aqueoushydrazinewithnitrous acid:

N₂H₄+ HNO₂→ HN₃+ 2 H₂O

With thehydraziniumcation[N₂H₅]⁺this reaction is written as:

[N₂H₅]⁺+ HNO₂→ HN₃+ H₂O + [H₃O]⁺

Other oxidizing agents, such ashydrogen peroxide,nitrosyl chloride,trichloramineornitric acid,can also be used to produce hydrazoic acid from hydrazine.^[10]

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.^[2]It is a weak acid (pK_a= 4.75.^[6]) Its heavy metal salts are explosive and readily interact with thealkyl iodides.Azides of heavieralkali metals(excludinglithium) oralkaline earth metalsare not explosive, but decompose in a more controlled way upon heating, releasing spectroscopically-pureN₂gas.^[12]Solutions of hydrazoic acid dissolve many metals (e.g.zinc,iron) with liberation of hydrogen and formation of salts, which are calledazides(formerly also called azoimides or hydrazoates).

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 calledSchmidt reactionor 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]⁺isisoelectronictodiazomethaneH₂C=N⁺=N⁻.

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 violentheadaches.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 treatingfurfuralwith a mixture of hydrazoic acid (HN₃) andperchloric acid(HClO₄) in the presence of magnesium perchlorate in thebenzenesolution at 35 °C.^[15]^[16]

Theall gas-phase iodine laser(AGIL) mixes gaseous hydrazoic acid withchlorineto produce excitednitrogen chloride,which is then used to causeiodineto lase; this avoids the liquid chemistry requirements ofCOIL lasers.

References

^Pradyot Patnaik.Handbook of Inorganic Chemicals.McGraw-Hill, 2002,ISBN 0-07-049439-8
^^a ^b ^cChisholm, Hugh,ed. (1911)."Azoimide".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.
^Curtius, Theodor(1890)."Ueber Stickstoffwasserstoffsäure (Azoimid) N₃H "[On hydrazoic acid (azoimide) N₃H].Berichte der Deutschen Chemischen Gesellschaft.23(2): 3023–3033.doi:10.1002/cber.189002302232.
^Furman, David; Dubnikova, Faina; van Duin, Adri C. T.; Zeiri, Yehuda; Kosloff, Ronnie (2016-03-10). "Reactive Force Field for Liquid Hydrazoic Acid with Applications to Detonation Chemistry".The Journal of Physical Chemistry C.120(9): 4744–4752.Bibcode:2016APS..MARH20013F.doi:10.1021/acs.jpcc.5b10812.ISSN 1932-7447.S2CID 102029987.
^^a ^bCatherine 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.
^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.
^Greenwood, Norman N.;Earnshaw, Alan (1997).Chemistry of the Elements(2nd ed.).Butterworth-Heinemann.p. 432.ISBN 978-0-08-037941-8.
^Greenwood, pp. 461–464.
^^a ^bEgon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). "The Nitrogen Group".Inorganic chemistry.Academic Press. p. 625.ISBN 978-0-12-352651-9.
^Foy, B.R.; Casassa, M.P.; Stephenson, J.C.; King, D.S. (1990). "Overtone-excitedHN
₃(X1A') - Anharmonic resonance, homogeneous linewidths, and dissociation rates ".Journal of Chemical Physics.92:2782–2789.doi:10.1063/1.457924.
^Besora, M.; Harvey, J.N. (2008). "Understanding the rate of spin-forbidden thermolysis ofHN
₃andCH
₃N
₃".Journal of Chemical Physics.129(4): 044303.doi:10.1063/1.2953697.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.
^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.S2CID 98593006.

External links

Media related toHydrogen azideat Wikimedia Commons
OSHA: Hydrazoic Acid Archived2008-04-04 at theWayback Machine

[1] Pradyot Patnaik.Handbook of Inorganic Chemicals.McGraw-Hill, 2002,ISBN 0-07-049439-8

[EB1911-2] Chisholm, Hugh,ed. (1911)."Azoimide".Encyclopædia Britannica.Vol. 3 (11th ed.). Cambridge University Press. pp. 82–83.This also contains a detailed description of the contemporaneous production process.

[3] Dictionary of Inorganic and Organometallic Compounds.Chapman & Hall.

[4] Curtius, Theodor(1890)."Ueber Stickstoffwasserstoffsäure (Azoimid) N₃H "[On hydrazoic acid (azoimide) N₃H].Berichte der Deutschen Chemischen Gesellschaft.23(2): 3023–3033.doi:10.1002/cber.189002302232.

[5] Furman, David; Dubnikova, Faina; van Duin, Adri C. T.; Zeiri, Yehuda; Kosloff, Ronnie (2016-03-10). "Reactive Force Field for Liquid Hydrazoic Acid with Applications to Detonation Chemistry".The Journal of Physical Chemistry C.120(9): 4744–4752.Bibcode:2016APS..MARH20013F.doi:10.1021/acs.jpcc.5b10812.ISSN 1932-7447.S2CID 102029987.

[InorgChem-6] 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.

[7] Gonzalez-Bobes, F. et al Org. Process Res. Dev. 2012, 16, 2051-2057.

[8] Treitler, D. S. et al Org. Process Res. Dev. 2017, 21, 460-467.

[9] L. F. Audrieth, C. F. Gibbs Hydrogen Azide in Aqueous and Ethereal Solution "Inorganic Syntheses 1939, vol. 1, pp. 71-79.

[10] Greenwood, Norman N.;Earnshaw, Alan (1997).Chemistry of the Elements(2nd ed.).Butterworth-Heinemann.p. 432.ISBN 978-0-08-037941-8.

[p461-11] Greenwood, pp. 461–464.

[wiberg-12] Egon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). "The Nitrogen Group".Inorganic chemistry.Academic Press. p. 625.ISBN 978-0-12-352651-9.

[13] Foy, B.R.; Casassa, M.P.; Stephenson, J.C.; King, D.S. (1990). "Overtone-excitedHN
₃(X1A') - Anharmonic resonance, homogeneous linewidths, and dissociation rates ".Journal of Chemical Physics.92:2782–2789.doi:10.1063/1.457924.

[14] Besora, M.; Harvey, J.N. (2008). "Understanding the rate of spin-forbidden thermolysis ofHN
₃andCH
₃N
₃".Journal of Chemical Physics.129(4): 044303.doi:10.1063/1.2953697.PMID 18681642.

[15] P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine".Khimiya Geterotsiklicheskikh Soedinenii.2:181–186.

[16] 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.S2CID 98593006.

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