Azides safety

I. Kabek and S. Urman, "Hazards of Copper Azide ia Fuzes," ia Minutes of the 14th Annual Explosives Safety Seminar, NTIS, 1972, p. 533. 

Automobile safety air bags use sodium azide [26628-22-8] NaN, for gas generation. It can be made from hydrazine by refluxing ethyl or Abutyl nitrite with hydrazine hydrate and sodium hydroxide in alcohol (209,210) ... 

Boron mixed with an oxidizer is used as a pyrotechnic. This ordnance appHcation for missiles and rockets is predominandy military. However, boron is also used in air bags, placed in automobiles as safety devices, for initiating the sodium azide [26628-22-8] which fiHs the bag with nitrogen (13). Other boron compounds are also used in the air-bag pyrotechnic appHcation. 

Although several interesting nitrogen-centered nucleophiles have been developed with ARO reactions of epoxides (vide supra), kinetic resolutions with such reagents are unlikely to be of practical value for the recovery of enantioenriched terminal epoxides. This is due to the fact that these nucleophiles are too valuable to be discarded in a by-product of the resolution, are generally not atom-economical, and, particularly in the case of azide, may represent safety hazards. 

It is difficult to obtain accurate particle size analyses of primary expls because (1) consideration and acceptance of necessary safety precautions make the usually tedious job of particle size analysis even more tedious, and (2) many primary expls used in production contain particles which are non-spherical in shape and are in the subsieve size range. Dry screening Lead Azide, for instance, is hazardous and must be done remotely. Furthermore, static charges... 

The pyrotechnic literature does not contain a critical evaluation of the ignition response time. of primary initiators in terms of their compn, temp tolerance and shock sensitivity. In general, primary expls such as Pb Azide or styphnate are selected whenever a brief (microsecond) response is desired, while, for instance, Pb thiocyanate-chlorate mixts are selected when high temps and high radiation environments are encountered, and presumably a longer ignition delay is the price which is paid for the extra margin of safety... 

Air bags, which act as safety devices in cars, contain solid sodinm azide. On impact, the sodium azide releases nitrogen gas, which expands the air bag. The main benefit of using a gas instead of another type of matter is that —... 

Use of sodium azide to introduce the nitrogen atom Safety issues surrounding sodium azide and hydrazoic acid... 

With a common intermediate from the Medicinal Chemistry synthesis now in hand in enantiomerically upgraded form, optimization of the conversion to the amine was addressed, with particular emphasis on safety evaluation of the azide displacement step (Scheme 9.7). Hence, alcohol 6 was reacted with methanesul-fonyl chloride in the presence of triethylamine to afford a 95% yield of the desired mesylate as an oil. Displacement of the mesylate using sodium azide in DMF afforded azide 7 in around 85% assay yield. However, a major by-product of the reaction was found to be alkene 17, formed from an elimination pathway with concomitant formation of the hazardous hydrazoic acid. To evaluate this potential safety hazard for process scale-up, online FTIR was used to monitor the presence of hydrazoic acid in the head-space, confirming that this was indeed formed during the reaction [7]. It was also observed that the amount of hydrazoic acid in the headspace could be completely suppressed by the addition of an organic base such as diisopropylethylamine to the reaction, with the use of inorganic bases such as... 

Sodium azide remains the source of nitrogen, however a thorough evaluation of the safety issues was conducted and safe operating conditions defined. 

Safety issues Use of sodium azide No known issues... 

Commercially, lead azide is usually manufactured by precipitation in the presence of dextrine, which considerably modifies the crystalline nature of the product. The procedure adopted is to add a solution of dextrine to the reaction vessel, often with a proportion of the lead nitrate or lead acetate required in the reaction. The bulk solutions of lead nitrate and of sodium azide are, for safety reasons, usually in vessels on the opposite sides of a blast barrier. They are run into the reaction vessel at a controlled rate, the whole process being conducted remotely under conditions of safety for the operator. When precipitation is complete, the stirring is stopped and the precipitate allowed to settle the mother liquor is then decanted. The precipitate is washed several times with water until pure. The product contains about 95% lead azide and consists of rounded granules composed of small lead azide crystals it is as safe as most initiating explosives and can readily be handled with due care. 

Many other methods of making lead azide in a safe form have been described, but the only one to have found commercial importance consists of replacing the dextrine by a small proportion of gelatine. When properly made this form of lead azide is as safe to handle as the dextrinated form and has improved sensitiveness to flame. It can therefore be used by itself in electric and delay detonators, but not in plain detonators as it is not ignited with certainty by safety fuse. 

The initiating explosive used must ignite with certainty from the spit of a safety fuse. It must be remembered that the intensity of the spit can be reduced if the safety fuse is not cut squarely and also that the fuse may in practice not always be fully inserted into the detonator. Lead azide by itself is not sufficiently easily ignited to give a satisfactory plain detonator and it is therefore used in admixture with lead styphnate, which is very readily ignited by flame. The proportions of such mixtures vary from 25 to 50% of lead styphnate. Mercury fulminate and diazodinitrophenol are sufficiently sensitive to flame not to require such additives. 

The normal initiating charge in a British detonator is lead azide modified with gelatine. In the case of plain detonators a small proportion of lead styphnate is added to the azide to ensure satisfactory ignition from safety fuse. 

It is a promising replacement for lead azide in detonators [1], and a remotely controlled procedure for the preparation of this oxygen-balanced compound is described [2]. Preparative methods have been assessed for safety features [3]. 

See REACTION SAFETY CALORIMETRY See Other POLYNITROARYL COMPOUNDS 3243. 6-Quinolinecarbonyl azide... 

The endothermic nitride is susceptible to explosive decomposition on friction, shock or heating above 100°C [1], Explosion is violent if initiated by a detonator [2], Sensitivity toward heat and shock increases with purity. Preparative precautions have been detailed [3], and further improvements in safety procedures and handling described [4], An improved plasma pyrolysis procedure to produce poly (sulfur nitride) films has been described [5], Light crushing of a small sample of impure material (m.p. below 160°C, supposedly of relatively low sensitivity) prior to purification by sublimation led to a violent explosion [6] and a restatement of the need [4] for adequate precautions. Explosive sensitivity tests have shown it to be more sensitive to impact and friction than is lead azide, used in detonators. Spark-sensitivity is, however, relatively low [7],... 

The following operations should be done using standard safety procedures for working with radioactive compounds. All steps involving SASD prior to initiation of the photoreaction should be done protected from light to avoid loss of phenyl azide activity. The radiolabeling procedure should be done quickly to prevent excessive loss of NHS ester activity due to hydrolysis. 

Numbers 7 and 8 in Table 3.6 represent high hazard substances such as azides, peroxides, perchlorates, and nitro compounds. The handling of such materials requires extreme care and safety precautions. 

Detonators are used to detonate high explosives. Stab detonators are initiated by sharp firing pins and are used in explosive trains of different types of fuses. Flash detonators are initiated by flames produced by safety fuses, primers, or delay elements. A special type of flash detonator ignited by the flame of a safety fuse is called a blasting cap. Detonators are primarily composed of three types of explosives including sinoxid mixtures, lead azide-based mixtures, and mercury fulminate-based mixtures. 

There are three anions that may loosely claim to be nitrides. Pentazolides (salts of cyclic N ) will all be explosive. Some azides (salts of N3) fall just short of being explosive but all are violently unstable. The true nitrides, nominal derivatives of N3-, are more various. In addition to some ionic structures, there are polymeric covalent examples, and some monomeric covalent ones, while most of those of transition metals are best considered as alloys. Several are endothermic and explosive, almost all are thermodynamically very unstable in air with respect to the oxide. Many are therefore pyrophoric if finely divided and also may react violently with water and, more particularly, acids, especially oxidising acids. A few are of considerable kinetic stability in these circumstances. There is no very clear classification of probable safety by position in the periodic table but polymeric and alloy structures are in general the more stable. Individual nitrides having entries ... 

Ring-opening by azide and the subsequent work-up is not ideal from a point of view of safety and costs and ring-opening by other nucleophiles is attractive. Furthermore, the use of meso compounds restricts the use of the catalyst to a small number of substrates and useful products. 

Sodium azide (NaN ) is an explosive salt of nitrogen that produces large quantities of gas upon its explosion. This quality has made it ideal as the chemical contained in automobile air safety bags. When triggered it explodes immediately, producing the expanding gases that fill the bag. 

Sodium azide is used to make lead azide and hydrazoic acid, and as a propellant for automotive safety bags. It also is used as an antihypertensive agent to control blood pressure. 

It becomes a problem in semantics to set a time limit for "development within which a process can be considered "spontaneous or "instantaneous . These two words seem to apply well to such extremely sensitive compounds as Nitrogen Triodide and Cupric Azide, which explode at the slightest touch when dry and, in addition, explode at a fairly low temperature. Attempts to correlate initiation in such cases with the attainment of a certain temperature seem unrealistic, especially in view of differences between relative sensitivity of different compounds to mechanical and thermal influences. For example, Mercuric Azide is so sensitive to impact that it explodes even under water, hut its heat sensitiveness is about the same as that for Cadmium Azide, which has been reported not to explode by percussion (Ref 5) Information about susceptibility of different explosives to spontaneous detonation is highly important from the viewpoint of safety. In Refs which follow are listed examples of spontaneous detonations of substances, some of them previously considered safe in this respect... 

Fleischer Burtle (Ref 3) give results for a flame test for different types ofLead Azide. In this test a std safety fuse provides the flame and percent firing of the Lead Azides is recorded as a function of distance from the fuse as shown in the tabulation below ... 

Nevertheless, examination of the response of explosives to more or less controlled impacts did provide qualitative information about the safety of handling these explosives. There is no question that Lead Azide is much more impact sensitive than TNT, and that TNT is much safer to handle than Lead Azide. It is the quantitative meaning of the much more" that creates confusion and indeed it may have no quantitative meaning at all. Presumably some of the immense effort devoted in past years to impact testing is excusable because it was based on the fond hope (unfortunately unrealized) of finding the ideal explosive—one that is powerful but insensitive ... 

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