Reactive Chemical Hazards of Azide Compounds: a Case Study and Lessons Learned

While a researcher was servicing a vacuum pump an unintended detonation occurred. This pump had been used in a sulfonyl azide synthesis (R-SO₂-N₃). The detonation occurred when he was applying effort to the hose barb from the outlet of the pump to connect it with a rubber hose. Differential Scanning Calorimetry (DSC) and headspace Gas Chromatography/Mass Spectrometry (GC/MS) were employed for the root cause investigation. The DSC showed a large exothermic decomposition (-1388J/g) for the residual sample from the pump fitting. Headspace GC/MS identified the presence of hydrazoic acid in the pump oil. The investigation concluded that either the azide precursor (sodium azide) or hydrolysis of the product (sulfonyl azide) was responsible for generating hydrazoic acid, which escaped from the dry ice trap and appeared in the downstream equipment, and probably reacted with metal parts (brass) to form a highly shock sensitive material (copper azide).  

This paper reviews the reactive chemical hazards for azide compounds involved in this case study.  Sodium azide is not particularly sensitive to mechanical impact, but its propensity to form hydrazoic acid in water is well-known, even at neutral pH. Likewise, the test data on sulfonyl azide product showed that it is not particularly sensitive to mechanical impact, but it can generate hydrazoic acid upon hydrolysis with water.  Metal azides which are formed by the reaction between hydrazoic acid and metal surfaces of equipment parts are highly hazardous due to their extreme impact and friction sensitivity.

Based on lessons learned, this paper also describes further steps for synthesizing organic azides using aqueous sodium azide.  These steps include, but are not limited to: (1) Utilizing a dedicated hood and equipments to limit potential HN₃ vapor streams from contacting any reactive metal surfaces. (2) Using a dual caustic trap system designed to scrub the outlet gases swept from the azide reaction step, instead of dry ice trap. (3) Using a 5% aqueous solution of ceric ammonium nitrate as a decontaminating agent for metal surfaces inside the fume hood at the completion of the campaign.  (4) Eliminating all brass or copper fittings from equipment used in the synthesis, due to the potential formation of the unstable explosive copper azide that can form from exposure of brass or copper parts to HN₃.