Sodium azide

Preparation

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

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 produces about 250 tons per year in 2004, with production increasing due to the increased use of airbags.

Laboratory methods

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.

3 NaNH₂ + NaNO₃ → NaN₃ + 3 NaOH + NH₃

Chemical reactions

Acid formation of hydrazoic acid

Treatment of sodium azide with strong acids gives hydrazoic acid (hydrogen azide; HN₃):

H⁺ + N−3 → HN₃

Hydrazoic acid, which is also extremely toxic, is especially dangerous because it is a volatile liquid at room temperature. Otherwise, aqueous solutions contain only minute amounts of hydrazoic acid, as described by the following equilibrium reaction:

N−3 + H₂O ⇌ HN₃ + OH⁻, K = 10^−4.6

Destruction

Sodium azide can be destroyed by treatment with nitrous acid (HNO₂) generated in situ from a solution of NaN₃ with a metal nitrite by acidification with a mineral acid.

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

A safer modification to the above method that avoids the potential production of hydrazoic acid or nitrogen oxide fumes is that of W. F. Rinkenbach. A solution of 2.5 oz (71 g) sodium nitrite in 1 US pt (470 mL) of water is added to a stirring dispersion of 1 oz (28 g) sodium azide in 1.5 US gal (5.7 L) 10% ammonium acetate, followed by addition of 7 US fl oz (210 mL) of glacial acetic acid. The solution is allowed to stand in a warm place for an hour and disposed of.

Applications

Automobile airbags and aircraft evacuation slides

Airbag formulations through late 1990s to early 2000s 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. While sodium azide is still used in evacuation slides on modern aircraft, newer-generation automotive air bags contain less sensitive explosives such as nitroguanidine or guanidine nitrate.

Organic and inorganic synthesis

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. 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 sulfide in pyridine. Oseltamivir, an antiviral medication, is currently produced in commercial scale by a method which utilizes sodium azide.

Sodium azide is a versatile precursor to other inorganic azide compounds, e.g., lead azide and silver azide, which are used in detonators as primary 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 also can react with the chloride salts of certain alkaline earth metals in aqueous solution, such as barium chloride or strontium 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

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.

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

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 oxidase in gram-negative bacteria; however, some gram-positive bacteria (streptococci, pneumococci, lactobacilli) are intrinsically resistant.

Agricultural uses

It is used in agriculture for pest control of soil-borne pathogens such as Meloidogyne incognita or Helicotylenchus dihystera.

It is also used as a mutagen for crop selection of plants such as rice, barley or oats.

Safety considerations

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

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

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.

Intentional consumption

Sodium azide has gained attention in the Netherlands and abroad 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 an illicit substance used as a suicide aid commonly called drug X (Dutch: middel X) In 2021, a review of all case reports of sodium azide intoxication indicated that 37% of cases were suicide attempts. An increase in the usage of sodium azide as a suicide drug has been attributed to its availability through pyrotechnics-focused online stores.

Treatment

The US CDC reports no specific antidote for azide poisoning. A 2021 narrative review identifies several cases of survival from ingestion when the patient is treated with antidotes for cyanide poisoning. From a mechanistic standpoint, hydroxocobalamin is more likely to be helpful than other antidotes such as sodium nitrite and sodium thiosulfate. As a result, the recommended treatment is hemodynamic support and hydroxocobalamin. First responders should use personal protection equipment to protect themselves from azide exposure.