Explosion reflux reaction

Fit a 3-litre rovmd-bottomed flask with a long reflux condenser and a dropping funnel (1). Place a mixture of 400 ml. of concentrated nitric acid and 600 ml. of water in the flask and heat nearly to boiling. Allow 100 g. (116 ml.) of cycZopentanone (Section 111,73) to enter the hot acid dropwise, taking care that the first few drops are acted upon by the acid, otherwise an explosion may occur the addition is complete in 1 hour. Much heat is evolved in the reaction so that the flame beneath the flask must be considerably lowered. Omng to the evolution of nitrons fumes, the reaction should be carried out in the fume cupboard or the fumes... 

CAUTION. The preparation of o-nitrobenzoyl chloride, o-nitrophenacetyl chloride and all o nitroacid chlorides should not be attempted by the above methods a violent explosion may occur upon distilling the product or when the last traces of thionyl chloride are removed in vacuo at 100°. Perhaps the safest method is to treat the pure acid in benzene solution with 1 1 mols of thionyl chloride and to reflux until evolution of sulphur dioxide and hydrogen chloride has ceased the solution of the acid chloride in benzene may then bo employed for most reactions. 

The first stage of a reaction involved the addition of sodium dispersed in toluene to a solution of adipic ester in toluene. The subsequent addition of iodomethane (b.p. 42°C) was too fast and vigorous boiling ejected some of the flask contents. Exposure of sodium particles to air caused ignition, and a violent toluene-air explosion followed [ 1 ]. When a reagent as volatile and reactive as iodomethane is added to a hot reaction mixture, controlled addition, and one or more wide-bore reflux condensers are essential. A similar incident involving benzene was also reported [2]. 

On the first full-scale run of a modified process for the nickel catalysed isomerisation of the oxime to the corresponding amide, on 1200 kg scale in toluene solution under reflux in place of the previous water, the reaction overheated (to >180°C), pressurised, and then escaped confinement. Investigation showed the explosion to be purely a runaway reaction caused by a slower start than previously. It was recommended that the oxime be charged in portions, and the solvent changed to the higher-boiling xylene. 

During preparation of acetic acid by acid dichromate oxidation of ethanol according to a published procedure, minor explosions occurred on two occasions after refluxing had been discontinued. This possibly may have involved formation of acetaldehyde (which has an AIT of 140°C) and ingress of air into the reaction vessel as it cooled [1]. Runaway reactions during small scale oxidation of ethanol have apparently been experienced by many teachers, poor initial mixing or starting too cool may be the cause [2],... 

The preparation and immediate use of manganese(III) azide species generated slowly in situ by refluxing manganese(III) acetate and sodium azide in acetic acid in presence of alkene reaction substrates to prepare 1,2-diazidoalkanes avoids the need to isolate manganese(III) azide which has a high probability of explosive instability [1]. The (II) azide is known [20260-90-6], isolable, detonable and has been patented as a power source for lasers [2],... 

If the boiling point is attained during runaway, a possible secondary effect of the evaporation of a solvent is the formation of an explosive vapor cloud, which in turn can lead to a severe explosion if ignited. In some cases, there is enough solvent present in the reaction mixture to compensate the energy release, allowing the temperature to stabilize at the boiling point. This is only possible if the solvent can be safely refluxed or distilled off into a catch pot or a scrubber. Moreover, the... 

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