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Revision as of 12:11, 9 August 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'ChEBI').← Previous edit		Latest revision as of 13:43, 14 December 2024 edit undo91.139.213.126 (talk) Different N-atoms in HN3 have different oxidation states: –1, +1, –1.
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			{{Short description|Unstable and toxic chemical compound}}
	{{chembox
			{{Chembox
	| verifiedrevid = 415301727
			| verifiedrevid = 443860054
	| Name = Hydrazoic acid
			| Name = Hydrazoic acid
	| ImageFile = Hydrogen-azide-2D-dimensions.png
			| ImageFile = Hydrogen-azide-2D-dimensions.png
	<!-- | ImageSize = 200px -->
	| ImageName = Structure, bonding and dimensions of the hydrogen azide molecule		| ImageName = Structure, bonding and dimensions of the hydrogen azide molecule
	| ImageFile1 = Hydrazoic_acid.svg		| ImageFile1 = Hydrazoic_acid.svg
			| ImageName1 = Hydrazoic acid
	| ImageName1 =
	| ImageFile2 = Hydrogen-azide-3D-vdW.png		| ImageFile2 = Hydrogen-azide-3D-vdW.png
	| ImageName2 = Hydrazoic acid		| ImageName2 = Hydrazoic acid
			| IUPACName = Hydrogen azide
	<!-- | ImageSize1 = 150px -->
			| OtherNames = Hydrogen azide<br>Azoimide<br>Azic acid
	| ImageName1 = Hydrazoic acid
			| Section1 = {{Chembox Identifiers
	| IUPACName = Hydrogen azide
			| ChEBI_Ref = {{ebicite|correct|EBI}}
	| OtherNames =
			| ChEBI = 29449
	| Section1 = {{Chembox Identifiers
	| ChEBI = 29449		| EINECS = 231-965-8
	| SMILES = ==		| SMILES = ==N
			| SMILES1 = N#
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
			| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 22937		| ChemSpiderID = 22937
	| InChI = 1/HN3/c1-3-2/h1H		| InChI = 1/HN3/c1-3-2/h1H
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	| ChEMBL_Ref = {{ebicite|correct|EBI}}		| ChEMBL_Ref = {{ebicite|correct|EBI}}
	| ChEMBL = 186537		| ChEMBL = 186537
			| Gmelin = 773
	| StdInChI_Ref = {{stdinchicite|correct|chemspider}}		| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChI = 1S/HN3/c1-3-2/h1H		| StdInChI = 1S/HN3/c1-3-2/h1H
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	| StdInChIKey = JUINSXZKUKVTMD-UHFFFAOYSA-N		| StdInChIKey = JUINSXZKUKVTMD-UHFFFAOYSA-N
	| CASNo = 7782-79-8		| CASNo = 7782-79-8
	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
			| UNII_Ref = {{fdacite|correct|FDA}}
	| RTECS =
	| PubChem = 24530		| UNII = 6P5C4D5D7I
			| RTECS =
	}}
			| PubChem = 24530
	| Section2 = {{Chembox Properties
			}}
	| Formula = HN<sub>3</sub>
			| Section2 = {{Chembox Properties
	| Appearance = colorless, highly volatile liquid
			| H=1|N=3
	| MolarMass = 43.03 g/mol
	| Density = 1.09 g/cm<sup>3</sup>		| Appearance = colorless, highly volatile liquid| Density = 1.09 g/cm<sup>3</sup>
	| Solubility = highly soluble		| Solubility = highly soluble
	| SolubleOther = soluble in ], ], ]		| SolubleOther = soluble in ], ], ]
	| MeltingPtC = -80		| MeltingPtC = -80
	| BoilingPtC = 37		| BoilingPtC = 37
	| pKa = 4.6 <ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, ISBN 0070494398</ref>		| pKa = 4.6 <ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, {{ISBN|0-07-049439-8}}</ref>
			| ConjugateBase = ]
	| Viscosity =
			| Viscosity =
	}}
			}}
	| Section3 = {{Chembox Structure
			| Section3 = {{Chembox Structure
	| MolShape = approximately linear
			| MolShape = approximately linear
	| Dipole =
	}}		}}
	| Section7 = {{Chembox Hazards		| Section7 = {{Chembox Hazards
	| ExternalMSDS =		| ExternalSDS =
			| MainHazards = Highly toxic, explosive, reactive
	| EUIndex = Not listed
			| FlashPt =
	| MainHazards = Highly toxic, explosive
			| GHSPictograms = {{GHS01}}{{GHS07}}{{GHS08}}
	| FlashPt =
	| RPhrases =		| GHSSignalWord = Danger
			| HPhrases = {{H-phrases|200|319|335|370}}
	| SPhrases =
			| PPhrases = {{P-phrases|201|202|260|261|264|270|271|280|281|304+340|305+351+338|307+311|312|321|337+313|372|373|380|401|403+233|405|501}}
	}}
			| NFPA-H = 4
	| Section8 = {{Chembox Related
	| OtherAnions =		| NFPA-F = 0
			| NFPA-R = 3
	| OtherCations = ]
			}}
	| Function = ] ]s
			| Section8 = {{Chembox Related
	| OtherFunctn = ]<br/>]
	| OtherCpds =		| OtherAnions =
			| OtherCations = ]<br/>]<br/>]
	}}
			| OtherFunction_label = ] ]s
			| OtherFunction = ]<br/>]
			| OtherCompounds =
			}}
	}}		}}
	'''Hydrazoic acid''', also known as '''hydrogen azide''' or '''azoimide''',<ref>{{Wikisource1911Enc Citation|Azoimide}}</ref> is a colorless, volatile, and extremely explosive liquid at room temperature and pressure. It is a compound of ] and ], having chemical formula HN<sub>3</sub>.<ref>{{cite book | title = Dictionary of Inorganic and Organometallic Compounds | publisher = Chapman &amp; Hall }}</ref> It was first isolated in 1890 by ].<ref>{{Cite journal | last = Curtius | first = Theodor | authorlink = Theodor Curtius | journal = Berichte | year = 1890 | page = 3023 | volume = 23}}</ref> It is used primarily for preservation of ]s, and as a reagent.		'''Hydrazoic acid''', also known as '''hydrogen azide''', '''azic acid''' or '''azoimide''',<ref name="EB1911">{{Cite EB1911 |wstitle=Azoimide |volume=3 |pages=82–83}} This also contains a detailed description of the contemporaneous production process.</ref> is a compound with the chemical formula {{chem2|HN3}}.<ref>{{cite book | title = Dictionary of Inorganic and Organometallic Compounds | publisher = Chapman & Hall }}</ref> It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of ] and ], and is therefore a ]. It was first isolated in 1890 by ].<ref>{{Cite journal | last = Curtius | first = Theodor | author-link = Theodor Curtius | title = Ueber Stickstoffwasserstoffsäure (Azoimid) N<sub>3</sub>H |trans-title=On hydrazoic acid (azoimide) N<sub>3</sub>H | journal = Berichte der Deutschen Chemischen Gesellschaft | year = 1890 | volume = 23 | issue = 2 | pages = 3023–3033 | url = http://babel.hathitrust.org/cgi/pt?id=umn.319510006827352;view=1up;seq=919 | doi=10.1002/cber.189002302232}}</ref> The acid has few applications, but its ], the ] ion, is useful in specialized processes.
			Hydrazoic acid, like its fellow ]s, is soluble in water. Undiluted hydrazoic acid is dangerously explosive<ref>{{Cite journal|last1=Furman|first1=David|last2=Dubnikova|first2=Faina|last3=van Duin|first3=Adri C. T.|last4=Zeiri|first4=Yehuda|last5=Kosloff|first5=Ronnie|date=2016-03-10|title=Reactive Force Field for Liquid Hydrazoic Acid with Applications to Detonation Chemistry|journal=The Journal of Physical Chemistry C|volume=120|issue=9|pages=4744–4752|doi=10.1021/acs.jpcc.5b10812|bibcode=2016APS..MARH20013F|s2cid=102029987 |issn=1932-7447}}</ref> with a ] Δ<sub>f</sub>H<sup>o</sup> (l, 298K) = +264 kJ/mol.<ref name="InorgChem" /> 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.<ref>Gonzalez-Bobes, F. et al Org. Process Res. Dev. 2012, 16, 2051-2057.</ref><ref>Treitler, D. S. et al Org. Process Res. Dev. 2017, 21, 460-467.</ref>
	==Chemistry==
	It is soluble in water, and the solution dissolves many metals (e.g. ], ]) with liberation of hydrogen and formation of salts (]s, formerly also called azoimides or hydrazoates).
			==Production==
	Its heavy metal salts are explosive and readily interact with the ]s. Azides of heavier ]s (excluding ]) or ]s are not explosive, but decompose in a more controlled way upon heating, releasing spectroscopically-pure {{chem|N|2}} gas.<ref name="wiberg"/>
			The acid is usually formed by acidification of an azide salt like ]. 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 ] as an extremely explosive colorless liquid with an unpleasant smell.<ref name="EB1911"/>
			:{{chem2|NaN3 + HCl → HN3 + NaCl}}
			Its aqueous solution can also be prepared by treatment of ] solution with dilute ], filtering the insoluble ].<ref>L . F. Audrieth, C. F. Gibbs Hydrogen Azide in Aqueous and Ethereal Solution" Inorganic Syntheses 1939, vol. 1, pp. 71-79.</ref>
			It was originally prepared by the reaction of aqueous ] with ]:
			:{{chem2|N2H4 + HNO2 → HN3 + 2 H2O}}
			With the ] cation {{chem2|+}} this reaction is written as:
			:{{chem2|+ + HNO2 → HN3 + H2O + +}}
			Other oxidizing agents, such as ], ], ] or ], can also be used to produce hydrazoic acid from hydrazine.<ref>{{Greenwood&Earnshaw2nd|page=432}}</ref>
			==Destruction prior to disposal==
			Hydrazoic acid reacts with nitrous acid:
			:{{chem2|HN3 + HNO2 → N2O + N2 + H2O}}
			This reaction is unusual in that it involves compounds with nitrogen in four different oxidation states.<ref name=p461>Greenwood, pp. 461–464.</ref>
			==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.<ref name="EB1911"/> It is a weak acid (p''K''<sub>a</sub>&nbsp;= 4.75.<ref name="InorgChem">{{cite book
			| title = Inorganic Chemistry, 3rd Edition
			| chapter = Chapter 15: The group 15 elements
			| author1 = Catherine E. Housecroft
			| author2 = Alan G. Sharpe
			| publisher = Pearson
			| year = 2008
			| isbn = 978-0-13-175553-6
			| page = 449
			}}</ref>) Its heavy metal salts are explosive and readily interact with the ]s. Azides of heavier ]s (excluding ]) or ]s are not explosive, but decompose in a more controlled way upon heating, releasing spectroscopically-pure {{chem2|N2}} gas.<ref name="wiberg"/> Solutions of hydrazoic acid dissolve many metals (e.g. ], ]) with liberation of hydrogen and formation of salts, which are called ]s (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 called ] or Schmidt rearrangement.
	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 (p''K''<sub>a</sub>&nbsp;= 4.6-4.7).
			]
			]
	Dissolution in the strongest acids produces explosive salts containing the {{chem|H|2|N&#x3D;N&#x3D;N|+}} ion, for example:<ref name="wiberg">{{cite book		Dissolution in the strongest acids produces explosive salts containing the aminodiazonium ion {{chem2|+ ⇌ +}}, for example:<ref name="wiberg">{{cite book
	| title = Inorganic chemistry		| title = Inorganic chemistry
	| chapter = The Nitrogen Group		| chapter = The Nitrogen Group
Line 81:		Line 123:
	| publisher = Academic Press		| publisher = Academic Press
	| year = 2001		| year = 2001
	| isbn = 0123526515		| isbn = 978-0-12-352651-9
	| page = 625		| page = 625
	}}</ref>		}}</ref>
	:{{chem|HN&#x3D;N&#x3D;N}} + {{chem|HSbCl|6}} → {{chem||+||-}}		:{{chem2|HN\dN\dN + H → +-}}
			The ion {{chem2|+}} is ] to ] {{chem2|H2C\dN+\dN-}}.
			The decomposition of hydrazoic acid, triggered by shock, friction, spark, etc. produces nitrogen and hydrogen:
	The ion {{chem|H|2|N&#x3D;N&#x3D;N|+}} is ] to ].
			:{{chem2|2 HN3 → H2 + 3 N2}}
	==Production==
	The acid is usually formed by acidification of an azide salt like ]. 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.
	:NaN<sub>3</sub>(s) + HCl(aq) → HN<sub>3</sub>(aq) + NaCl(aq)
			Hydrazoic acid undergoes unimolecular decomposition at sufficient energy:
	Can also be prepared by treatment of ] solution with dilute sulfuric acid, filtering the insoluble ].<ref name="Inorganic Synthesis Vol.1">{{cite book
	|author= Booth, Harold Simmons
			:{{chem2|HN3 → NH + N2}}
	|title=Inorganic Synthesis Vol.1
	|publisher=MCGRAW-HILL
			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.<ref>{{cite journal |last1=Foy |first1=B.R. |last2= Casassa |first2= M.P. |first3= J.C. |last3= Stephenson |first4= D.S. |last4= King |title = Overtone-excited {{chem|HN|3}} (X1A') - Anharmonic resonance, homogeneous linewidths, and dissociation rates |journal = Journal of Chemical Physics | year = 1990 | volume = 92 | pages = 2782–2789 |doi = 10.1063/1.457924}}</ref> In addition, these unimolecular rates have been analyzed theoretically, and the experimental and calculated rates are in reasonable agreement.<ref>{{cite journal |last1 = Besora |first1= M. |last2= Harvey |first2= J.N. |title = Understanding the rate of spin-forbidden thermolysis of {{chem|HN|3}} and {{chem|CH|3|N|3}} |journal = Journal of Chemical Physics | volume = 129 | pages = 044303 | year = 2008 |issue= 4 | doi=10.1063/1.2953697|pmid= 18681642 }}</ref>
	|location=
	|year=1939
	|pages=
	|isbn=9780470131602
	|oclc=
	|doi=10.1002/9780470132326
	|accessdate=
	}}</ref>
	==Toxicity==		==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.		Hydrazoic acid is volatile and highly toxic. It has a pungent smell and its vapor can cause violent ]s. The compound acts as a non-cumulative poison.
			==Applications==
			], a pharmaceutical intermediate and potential artificial sweetening agent has been prepared in good yield by treating ] with a mixture of hydrazoic acid ({{chem2|HN3}}) and ] ({{chem2|HClO4}}) in the presence of magnesium perchlorate in the ] solution at 35&nbsp;°C.<ref>{{cite journal | author = P. A. Pavlov | title = Synthesis of 5-substituted furannitriles and their reaction with hydrazine | journal = Khimiya Geterotsiklicheskikh Soedinenii | volume = 2 | pages = 181–186 | year = 1986 |last2 = Kul'nevich | first2 = V. G.}}</ref><ref>{{cite journal | author = B. Bandgar | title = Organic reactions in water. Transformation of aldehydes to nitriles using NBS under mild conditions | journal = Synthetic Communications | volume = 36 | pages = 1347–1352 | year = 2006 |last2 = Makone | first2 = S. | issue = 10 | doi=10.1080/00397910500522009| s2cid = 98593006 }}</ref>
			The ] (AGIL) mixes gaseous hydrazoic acid with ] to produce excited ], which is then used to cause ] to lase; this avoids the liquid chemistry requirements of ]s.
	==References==		==References==
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	==External links==		==External links==
			*{{Commonscatinline}}
	*
			* {{Webarchive|url=https://web.archive.org/web/20080404020425/http://www.osha.gov/dts/chemicalsampling/data/CH_245950.html |date=2008-04-04 }}
			{{Authority control}}
			{{Hydrides by group}}
			{{Azides}}
	]		]
	]		]
			]
			]
	]
			]
	]
			]
	]
	]
	]
	]
	]
	]
	]
	]
	]
	]
	]
	]
	]
	]