Explosives 2-butanone

The effect of the nitric acid/hydrogen peroxide mixture on acetone when it is hot gives rise to an explosive oxidation, especially when the medium is confined. This situation also applies to a large number of ketones, and in particular, cyclic ketones. Cyclic di- and triperoxides form compounds that detonate, if there is no strict and very delicate thermal control. Accidents have been reported with butanone, 3-pentanone, cyclopentanone, cyclohexanone and methylcyclo-hexanones. 

Dining distillation of 2-propanol recovered from the reduction of crotonaldehyde with isopropanol/aluminium isopropoxide, a violent explosion occurred. This was attributed to peroxidised diisopropyl ether (a possible by-product) or to peroxidised crotonaldehyde. An alternative or additional possibility is that the isopropanol may have contained traces of a higher secondary alcohol (e.g. 2-butanol) which would be oxidised during the Meerwein-Ponndorf reduction procedure to 2-butanone. The latter would then effectively sensitise the isopropanol or other peroxidisable species to peroxidation. 

Distillation to small volume of a small sample of a 4-year-old mixture of the alcohol with 0.5% of the ketone led to a violent explosion, and the presence of peroxides was subsequently confirmed [1]. Pure alcohols which can form stable radicals (secondary branched structures) may slowly peroxidise to a limited extent under normal storage conditions (isopropanol to 0.0015 M in brown bottle, subdued light during 6 months to 0.0009 M in dark during 5 years) [2], The presence of ketones markedly increases the possibility of peroxidation by sensitising photochemical oxidation of the alcohol. Acetone (produced during autoxidation of isopropanol) is not a good sensitiser, but the presence of even traces of 2-butanone in isopropanol would be expected to accelerate markedly peroxidation of the latter. Treatment of any mixture or old sample of a secondary alcohol with tin(II) chloride and then lime before distillation is recommended [3], The product of photosensitised oxidation is 2-hydroperoxy-2-propanol [4]. 

A powerful explosion which occurred dining distillation of a 10-year-old sample of the alcohol was attributed to presence of peroxy compounds formed by autoxidation, possibly involving 2-butanone as an effective photochemical sensitiser [1], After a later explosion, it was found that the sample being distilled contained 12% of peroxide [2], A further incident involved a 12-year old sample which exploded at the end of distillation, and which also contained a high level of peroxide. Several other stock alcohols were found to contain much lower levels of peroxide than the 2-butanol, and recommendations on clean-up or disposal, depending on the level of peroxide, are made [3], A further report of an explosion at the end of laboratory distillation confirms the potential for peroxide formation on prolonged storage of 2-butanol [4],... 

Secondary alcohols are readily autoxidised in contact with oxygen or air, forming ketones and hydrogen peroxide [1], A partly full bottle of 2-propanol exposed to sunlight for a long period became 0.36 M in peroxide and potentially explosive [2], See 2-Propanol 2-Butanone... 

Existing and proposed methods of evaluating transportation hazards of organic peroxides exposed to impact, explosive shock or thermal singe stimuli were reviewed, and a hazard classification system proposed [1]. Commercial 2-butanone peroxide ( MEK peroxide ) as a 40% solution in dimethyl phthalate was previously... 

Dining preparation of tris(ketoximino)silanes, two violent explosions attributed to acid-catalysed exothermic rearrangement/decomposition reactions occurred. Although these silane derivatives can be distilled under reduced pressure, the presence of acidic impurities (e.g. 2-butanone oxime hydrochloride, produced during silane preparation) drastically reduces thermal stability. Iron(III) chloride at 500 ppm caused degradation to occur at 150°, and at 2% concentration violent decomposition set in at 50°C. 

A TNT explosive was determined in the gas phase using an MIP-QCM chemosensor [127]. The MIP preparation procedure involved dissolution of an appropriate amount of the TNT template, MAA monomer, EGDMA cross-linker and Irgacure 369 [2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-l] photoinitiator... 

The total product of a batch containing a chlorotriazine, water, sodium hydroxide and 2-butanone had not been discharged from the 11,000 1 vessel when a further 1.5 t of cyanuric chloride was charged ready for the next batch. The ensuing rapid exothermic hydrolysis led to eruption of the reactor contents, ignition and explosion of butanone vapour, and damage of 3M dollars. 

Flammable liquid. A very dangerous fire hazard when exposed to heat, flame, or oxidizers. Moderately explosive when exposed to heat or flame. Reacts with air to form dangerous peroxides. The presence of 2-butanone increases the reaction rate for peroxide formation. Hydrogen peroxide sharply reduces the autoignition temperature. Violent explosive reaction when heated with aluminum isopropoxide + crotonaldehyde + heat. Forms explosive mixtures with trinitromethane, hydrogen... 

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