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Contents

   



(Top)
 


1 Structure  





2 Preparation  



2.1  Laboratory methods  







3 Chemical reactions  



3.1  Acid formation of hydrazoic acid  





3.2  Hydrazoic acid equilibrium  





3.3  Destruction  







4 Applications  



4.1  Automobile airbags and aircraft evacuation slides  





4.2  Organic and inorganic synthesis  





4.3  Biochemistry and biomedical uses  





4.4  Agricultural uses  







5 Safety considerations  



5.1  Intentional consumption  







6 References  





7 External links  














Sodium azide






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From Wikipedia, the free encyclopedia
 


Sodium azide
Names
IUPAC name

Sodium azide

Other names

Sodium trinitride
Smite
Azium

Identifiers

CAS Number

3D model (JSmol)

ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.043.487 Edit this at Wikidata
EC Number
  • 247-852-1

PubChem CID

RTECS number
  • VY8050000
UNII
UN number 1687

CompTox Dashboard (EPA)

  • InChI=1S/N3.Na/c1-3-2;/q-1;+1 checkY

    Key: PXIPVTKHYLBLMZ-UHFFFAOYSA-N checkY

  • InChI=1/N3.Na/c1-3-2;/q-1;+1

    Key: PXIPVTKHYLBLMZ-UHFFFAOYAH

  • [N-]=[N+]=[N-].[Na+]

Properties

Chemical formula

NaN3
Molar mass 65.0099 g/mol
Appearance Colorless to white solid
Odor Odorless
Density 1.846 g/cm3 (20 °C)
Melting point 275 °C (527 °F; 548 K) violent decomposition

Solubility in water

38.9 g/100 mL (0 °C)
40.8 g/100 mL (20 °C)
55.3 g/100 mL (100 °C)
Solubility Very soluble in ammonia
Slightly soluble in benzene
Insoluble in diethyl ether, acetone, hexane, chloroform
Solubilityinmethanol 2.48 g/100 mL (25 °C)
Solubilityinethanol 0.22 g/100 mL (0 °C)
Acidity (pKa) 4.8
Structure

Crystal structure

Hexagonal, hR12[1]

Space group

R-3m, No. 166
Thermochemistry

Heat capacity (C)

76.6 J/mol·K

Std molar
entropy
(S298)

70.5 J/mol·K

Std enthalpy of
formation
fH298)

21.3 kJ/mol

Gibbs free energy fG)

99.4 kJ/mol
Hazards
GHS labelling:

Pictograms

GHS01: Explosive GHS06: Toxic GHS08: Health hazard GHS09: Environmental hazard

Signal word

Danger

Hazard statements

H300, H310, H410

Precautionary statements

P260, P280, P301+P310, P501 [2]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
4
1
3
Flash point 300 °C (572 °F; 573 K)
Lethal dose or concentration (LD, LC):

LD50 (median dose)

27 mg/kg (oral, rats/mice)[1]
NIOSH (US health exposure limits):

PEL (Permissible)

None[3]

REL (Recommended)

C 0.1 ppm (asHN3) [skin]
C 0.3 mg/m3 (asNaN3) [skin][3]

IDLH (Immediate danger)

N.D.[3]
Safety data sheet (SDS) ICSC 0950
Related compounds

Other anions

Sodium cyanide

Other cations

Potassium azide
Ammonium azide

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

☒N verify (what is checkY☒N ?)

Infobox references

Sodium azide is an inorganic compound with the formula NaN3. This colorless salt is the gas-forming component in some car airbag systems. It is used for the preparation of other azide compounds. It is an ionic substance, is highly soluble in water, and is acutely poisonous.[5]

Structure[edit]

Sodium azide is an ionic solid. Two crystalline forms are known, rhombohedral and hexagonal.[1][6] Both adopt layered structures. The azide anion is very similar in each form, being centrosymmetric with N–N distances of 1.18 Å. The Na+ ion has an octahedral geometry. Each azide is linked to six Na+ centers, with three Na–N bonds to each terminal nitrogen center.[7]

Preparation[edit]

The common synthesis method is the "Wislicenus process", which proceeds in two steps in liquid ammonia. In the first step, ammonia is converted to sodium amide by metallic sodium:

2 Na + 2 NH3 → 2 NaNH2 + H2

It is a redox reaction in which metallic sodium gives an electron to a protonofammonia which is reduced in hydrogen gas. Sodium easily dissolves in liquid ammonia to produce solvated electrons responsible for the blue color of the resulting liquid. The Na+ and NH2 ions are produced by this reaction.

The sodium amide is subsequently combined with nitrous oxide:

2 NaNH2 + N2O → NaN3 + NaOH + NH3

These reactions are the basis of the industrial route, which produced about 250 tons per year in 2004, with production increasing due to the increased use of airbags.[5]

Laboratory methods[edit]

Curtius and Thiele developed another production process, where a nitrite ester is converted to sodium azide using hydrazine. This method is suited for laboratory preparation of sodium azide:

2 NaNO2 + 2 C2H5OH + H2SO4 → 2 C2H5ONO + Na2SO4 + 2 H2O
C2H5ONO + N2H4·H2O + NaOH → NaN3 + C2H5OH + 3 H2O

Alternatively the salt can be obtained by the reaction of sodium nitrate with sodium amide.[8]

3 NaNH2 + NaNO3 → NaN3 + 3 NaOH + NH3

Chemical reactions[edit]

Acid formation of hydrazoic acid[edit]

Treatment of sodium azide with strong acids gives gaseous hydrazoic acid (hydrogen azide; HN3), which is also extremely toxic:

H+ + N3 → HN3

Hydrazoic acid equilibrium[edit]

Aqueous solutions contain minute amounts of hydrazoic acid, the formation of which is described by the following equilibrium:

N3 + H2O ⇌ HN3 + OH, K = 10−4.6

Destruction[edit]

Sodium azide can be destroyed by treatment with in situ prepared nitrous acid (HNO2; not HNO3).[9][10] In situ preparation is necessary as HNO2 is unstable and decomposes rapidly in aqueous solutions. This destruction must be done with great caution and within a chemical fume hood as the formed gaseous nitric oxide (NO) is also toxic, and an incorrect order of acid addition for in situ formation of HNO2 will instead produce gaseous highly toxic hydrazoic acid (HN3).[9]

2 NaN3 + 2 HNO2 → 3 N2 + 2 NO + 2 NaOH

Applications[edit]

Automobile airbags and aircraft evacuation slides[edit]

Older airbag formulations contained mixtures of oxidizers, sodium azide and other agents including ignitors and accelerants. An electronic controller detonates this mixture during an automobile crash:

2 NaN3 → 2 Na + 3 N2

The same reaction occurs upon heating the salt to approximately 300 °C. The sodium that is formed is a potential hazard alone and, in automobile airbags, it is converted by reaction with other ingredients, such as potassium nitrate and silica. In the latter case, innocuous sodium silicates are generated.[11] While sodium azide is still used in evacuation slides on modern aircraft, newer-generation automotive air bags contain less sensitive explosives such as nitroguanidineorguanidine nitrate.[12]

Organic and inorganic synthesis[edit]

Due to its explosion hazard, sodium azide is of only limited value in industrial-scale organic synthesis. In the laboratory, it is used to introduce the azide functional group by displacement of halides.[10] The azide functional group can thereafter be converted to an amine by reduction with either SnCl2 in ethanol or lithium aluminium hydride or a tertiary phosphine, such as triphenylphosphine in the Staudinger reaction, with Raney nickel or with hydrogen sulfideinpyridine. Oseltamivir, an antiviral medication, is currently produced in commercial scale by a method which utilizes sodium azide.[13]

Sodium azide is a versatile precursor to other inorganic azide compounds, e.g., lead azide and silver azide, which are used in detonatorsasprimary explosives. These azides are significantly more sensitive to premature detonation than sodium azide and thus have limited applications. Lead and silver azide can be made via double displacement reaction with sodium azide and their respective nitrate (most commonly) or acetate salts. Sodium azide can also react with the chloride salts of certain alkaline earth metals in aqueous solution, such as barium chlorideorstrontium chloride to respectively produce barium azide and strontium azide, which are also relatively sensitive primarily explosive materials. These azides can be recovered from solution through careful desiccation.

Biochemistry and biomedical uses[edit]

Sodium azide is a useful probe reagent, and an antibacterial preservative for biochemical solutions. In the past merthiolate and chlorobutanol were also used as an alternative to azide for preservation of biochemical solutions.[14]

Sodium azide is an instantaneous inhibitor of lactoperoxidase, which can be useful to stop lactroperoxidase catalyzed 125I protein radiolabeling experiments.[15]

In hospitals and laboratories, it is a biocide; it is especially important in bulk reagents and stock solutions which may otherwise support bacterial growth where the sodium azide acts as a bacteriostatic by inhibiting cytochrome oxidaseingram-negative bacteria; however, some gram-positive bacteria (streptococci, pneumococci, lactobacilli) are intrinsically resistant.[16]

Agricultural uses[edit]

It is used in agriculture for pest control of soil-borne pathogens such as Meloidogyne incognitaorHelicotylenchus dihystera.[17]

It is also used as a mutagen for crop selection of plants such as rice,[18] barley[19] or oats.[20]

Safety considerations[edit]

Sodium azide can be fatally toxic,[21] and even minute amounts can cause symptoms. The toxicity of this compound is comparable to that of soluble alkali cyanides,[22] although no toxicity has been reported from spent airbags.[23]

It produces extrapyramidal symptoms with necrosis of the cerebral cortex, cerebellum, and basal ganglia. Toxicity may also include hypotension,[24] blindness and hepatic necrosis. Sodium azide increases cyclic GMP levels in the brain and liver by activation of guanylate cyclase.[25]

Sodium azide solutions react with metallic ions to precipitate metal azides, which can be shock sensitive and explosive. This should be considered for choosing a non-metallic transport container for sodium azide solutions in the laboratory. This can also create potentially dangerous situations if azide solutions should be directly disposed down the drain into a sanitary sewer system. Metal in the plumbing system could react, forming highly sensitive metal azide crystals which could accumulate over years. Adequate precautions are necessary for the safe and environmentally responsible disposal of azide solution residues.[26]

Intentional consumption[edit]

Sodium azide has gained attention in the Netherlands[27] and abroad[28] as a chemical used for homicidal and suicidal purposes.

Sodium azide has been attributed to at least 172 deaths in the period from 2015 to 2022 as part of a illicit substance used as a suicide aid commonly called drug X (Dutch: middel X)[29] In 2021, a review of all case reports of sodium azide intoxication indicated that 37% of cases were suicide attempts.[30] An increase in the usage of sodium azide as a suicide drug has been attributed to its availability through pyrotechnics-focused online stores.[31]

References[edit]

  1. ^ a b c Stevens E. D.; Hope H. (1977). "A Study of the Electron-Density Distribution in Sodium Azide, NaN
    3
    "
    . Acta Crystallographica A. 33 (5): 723–729. doi:10.1107/S0567739477001855.
  • ^ "Sodium azide".
  • ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0560". National Institute for Occupational Safety and Health (NIOSH).
  • ^ "Material Safety Data Sheet" (PDF). Sciencelab.com. November 6, 2008. Archived from the original (PDF) on March 4, 2016. Retrieved October 26, 2015.
  • ^ a b Jobelius, Horst H.; Scharff, Hans-Dieter (2000). "Hydrazoic Acid and Azides". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a13_193. ISBN 9783527306732.
  • ^ Wells, A. F. (1984), Structural Inorganic Chemistry (5th ed.), Oxford: Clarendon Press, ISBN 0-19-855370-6
  • ^ Pringle, G. E.; Noakes, D. E. (1968-02-15). "The crystal structures of lithium, sodium and strontium azides". Acta Crystallographica Section B. 24 (2): 262–269. Bibcode:1968AcCrB..24..262P. doi:10.1107/s0567740868002062.
  • ^ Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5.
  • ^ a b Committee on Prudent Practices for Handling, Storage, and Disposal of Chemicals in Laboratories, Board on Chemical Sciences and Technology, Commission on Physical Sciences, Mathematics, and Applications, National Research Council (1995). "Disposal of Waste". Prudent Practices in the Laboratory: Handling and Disposal of Chemicals. Washington, DC: National Academy Press. p. 165. ISBN 978-0-309-05229-0.{{cite book}}: CS1 maint: multiple names: authors list (link)
  • ^ a b Turnbull, Kenneth; Narsaiah, B.; Yadav, J. S.; Yakaiah, T.; Lingaiah, B. P. V. (2008-03-14), "Sodium Azide", Encyclopedia of Reagents for Organic Synthesis, Chichester, UK: John Wiley & Sons, Ltd, doi:10.1002/047084289x.rs045.pub2, ISBN 978-0471936237
  • ^ Betterton, E. A. (2003). "Environmental Fate of Sodium Azide Derived from Automobile Airbags". Critical Reviews in Environmental Science and Technology. 33 (4): 423–458. Bibcode:2003CREST..33..423B. doi:10.1080/10643380390245002. S2CID 96404307.
  • ^ Halford, Bethany (November 15, 2022). "What chemicals make airbags inflate, and how have they changed over time?". Chemical & Engineering News. 100 (41). Retrieved 4 June 2023. The chemical reaction used to deploy airbags has evolved, but one iteration resulted in massive recalls Open access icon
  • ^ Rohloff John C.; Kent Kenneth M.; Postich Michael J.; Becker Mark W.; Chapman Harlan H.; Kelly Daphne E.; Lew Willard; Louie Michael S.; McGee Lawrence R.; et al. (1998). "Practical Total Synthesis of the Anti-Influenza Drug GS-4104". J. Org. Chem. 63 (13): 4545–4550. doi:10.1021/jo980330q.
  • ^ Scopes, Robert K. (1994). Protein Purification. New York, NY: Springer New York. p. 204. doi:10.1007/978-1-4757-2333-5. ISBN 978-1-4419-2833-7.
  • ^ Deutscher, M.P. (1990). Guide to Protein Purification. Methods in enzymology. Academic Press. p. 729. ISBN 978-0-12-182083-1. Retrieved 2023-04-10.
  • ^ Lichstein, H. C.; Soule, M. H. (1943). "Studies of the Effect of Sodium Azide on Microbic Growth and Respiration: I. The Action of Sodium Azide on Microbic Growth". Journal of Bacteriology. 47 (3): 221–230. doi:10.1128/JB.47.3.221-230.1944. PMC 373901. PMID 16560767.
  • ^ Applications of sodium azide for control of soilborne pathogens in potatoes. Rodriguez-Kabana, R., Backman, P. A. and King, P.S., Plant Disease Reporter, 1975, Vol. 59, No. 6, pp. 528-532 (link)
  • ^ Awan, M. Afsar; Konzak, C. F.; Rutger, J. N.; Nilan, R. A. (2000-01-01). "Mutagenic Effects of Sodium Azide in Rice1". Crop Science. 20 (5): 663–668. doi:10.2135/cropsci1980.0011183x002000050030x.
  • ^ Cheng, Xiongying; Gao, Mingwei (1988). "Biological and genetic effects of combined treatments of sodium azide, gamma rays and EMS in barley". Environmental and Experimental Botany. 28 (4): 281–288. Bibcode:1988EnvEB..28..281C. doi:10.1016/0098-8472(88)90051-2.
  • ^ Rines, H. W. (1985-02-01). "Sodium azide mutagenesis in diploid and hexaploid oats and comparison with ethyl methanesulfonate treatments". Environmental and Experimental Botany. 25 (1): 7–16. Bibcode:1985EnvEB..25....7R. doi:10.1016/0098-8472(85)90043-7.
  • ^ Chang, Soju; Lamm, Steven H. (2003-05-01). "Human Health Effects of Sodium Azide Exposure: A Literature Review and Analysis". International Journal of Toxicology. 22 (3): 175–186. doi:10.1080/10915810305109. ISSN 1091-5818. PMID 12851150. S2CID 38664824.
  • ^ "MSDS: sodium azide". Mallinckrodt Baker. 2008-11-21. MSDS S2906.
  • ^ Olson, Kent; Anderson, Ilene B. (18 September 2006). Poisoning & Drug Overdose, 5th Edition. McGraw-Hill Companies, Incorporated. p. 123. ISBN 978-0-07-144333-3.
  • ^ Gordon, Steven M.; Drachman, Jonathan; Bland, Lee A.; Reid, Marie H.; Favero, Martin; Jarvis, William R. (1990-01-01). "Kidney International - Abstract of article: Epidemic hypotension in a dialysis center caused by sodium azide". Kidney Int. 37 (1): 110–115. doi:10.1038/ki.1990.15. ISSN 0085-2538. PMID 2299796.
  • ^ Kimura, Hiroshi; Mittal, Chandra K.; Murad, Ferid (1975-10-23). "Increases in cyclic GMP levels in brain and liver with sodium azide an activator of guanylate cyclase". Nature. 257 (5528): 700–702. Bibcode:1975Natur.257..700K. doi:10.1038/257700a0. PMID 241939. S2CID 115294.
  • ^ "Sodium Azide | Environmental Health & Safety | Northeastern University".
  • ^ Bruin, Maaike A. C.; Dekker, Douwe; Venekamp, Nikkie; Tibben, Matthijs; Rosing, Hilde; de Lange, Dylan W.; Beijnen, Jos H.; Huitema, Alwin D. R. (March 2021). "Toxicological analysis of azide and cyanide for azide intoxications using gas chromatography". Basic & Clinical Pharmacology & Toxicology. 128 (3): 534–541. doi:10.1111/bcpt.13523. ISSN 1742-7835. PMC 7984282. PMID 33090684.
  • ^ Конец скорпиона // Аргументы и факты
  • ^ "Zeker 172 mensen overleden door zelfdoding met middel X" [At least 172 people have died by suicide due to drug X]. NU.nl (in Dutch). 18 April 2024.
  • ^ Wachełko, Olga; Zawadzki, Marcin; Szpot, Paweł (2021-07-30). "A novel procedure for stabilization of azide in biological samples and method for its determination (HS-GC-FID/FID)". Scientific Reports. 11 (1): 15568. doi:10.1038/s41598-021-95104-5. ISSN 2045-2322. PMC 8324859. PMID 34330976.
  • ^ van der Heijden, Lisa T.; van den Hondel, Karen E.; Olyslager, Erik J. H.; de Jong, Lutea A. A.; Reijnders, Udo J. L.; Franssen, Eric J. F. (2023-07-13). "Internet-Purchased Sodium Azide Used in a Fatal Suicide Attempt: A Case Report and Review of the Literature". Toxics. 11 (7): 608. doi:10.3390/toxics11070608. ISSN 2305-6304. PMC 10385699. PMID 37505573.
  • External links[edit]


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