Oxidation with Ammonium Nitrate

In a 100-mL flask fitted with a reflux condenser are placed 0.1 g (0.0005 mol) of cupric acetate monohydrate (as a catalyst), 5 g (0.0625 mol) of ammonium nitrate, 10.6 g (0.05 mol) of benzoin, and 35 mL of 80% aqueous acetic acid. The mixture is heated with occasional shaking of the flask. Soon a vigorous evolution of nitrogen commences. After a 1.5-h reflux, the solution is cooled and seeded with a crystal of benzil (or by scratching the walls of the flask with a glass rod) until crystallization takes place. Water is added to the mixture to precipitate the residual benzil. The crystals are filtered with suction and washed with water containing about 20% of ethanol. The yield of benzil is quantitative. The melting point of the product after recrystallization from 70% ethanol is 95 °C. 

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Bertrand Pelletier (Bayonne, 30 July 1761-Paris, 21 July 1797 (after inhaling chlorine)) was first an assistant to D Arcet, then an apothecary, finally from 1795 professor in the ficole Polytechnique, and a member of government commissions. He worked on arsenic acid, which he obtained by heating arsenious oxide with ammonium nitrate, the crystallisation of deliquescent salts, chlorine, discovering chlorine hydrate independently of Berthollet (see p. 504), ethers, plumbago and molybdenite, and the preparation of phosphorus and its compounds, including phosphorous acid, phosphoric acid, and hydrogen phosphide (discovered by Gei embre) he was severely burned by an accident with phosphorus, which he showed would bum in air under water. He also published on strontium compounds, the analyses of... 

In World War II, foe Germans made use of otherwise unusable airplane parts by grinding them up into powdered aluminum. This was made to react with ammonium nitrate to produce powerful bombs. The products of this reaction were nitrogen gas, steam, and aluminum oxide. If 10.00 kg of ammonium nitrate is mixed with 10.00 kg of powdered aluminum, how much heat is generated ... 

Ammoniacal silver oxide is as dangerous as the previous similar compounds. Thus, the clear solution, which is obtained after centrifuging ammoniacal silver oxide leaves a very explosive compound as a residue to which was attributed the AgaN4 formula. It seems that the decomposition of this nitride is inhibited by ammonium salts. A similar situation was created after treating this ammoniacal oxide with silver nitrate until a solid started to precipitate, and this detonated 10 to 14 days after being prepared. It was assumed that this solid was AggNH. 

The title compound ( cyanamide dihydrochloride ) reacts with perchloric acid to form the perchlorate salt, and with ammonium nitrate, the nitrate salt, both being highly explosive, and the latter also an oxidant. 

Dave and co-workers have reported a successful synthesis of 2,2,4,4-tetranitroadamantane (117) which uses the mono-protected diketone (113) as a key intermediate. In this synthesis (113) is converted to the oxime (114) and then treated with ammonium nitrate and nitric acid in methylene chloride to yield the em-dinitro derivative (115). This nitration-oxidation step also removes the acetal-protecting group to leave the second ketone group free. Formation of the oxime (116) from ketone (115), followed by a similar nitration-oxidation with nitric acid and ammonium nitrate, yields 2,2,4,4-tetranitroadamantane (117). In this synthesis the protection strategy enables each carbonyl group to be treated separately and thus prevents the problem of internal nitroso dimer formation. 

Ceric ammonium nitrate is prepared by electrolytic oxidation of cerous nitrate in nitric acid to ceric nitrate, followed by the addition of ammonium nitrate solution. It is separated from the solution by crystaUization. It may be prepared alternatively by dissolving cerium(II) oxide, Ce0 H20 in concentrated nitric acid followed by treatment with ammonium nitrate. 

The latter is unstable and undergoes decomposition in hot water with the evolution of formaldehyde, nitrous oxide and ammonium nitrate... 

The explosive properties of mixtures with ammonium nitrate depend on the quantitative relationship between the oxidizing agent and the explosive or combustible substance. According to Parisot and Laffitte s [9, 47] investigations the explosive properties of mixtures of aromatic nitro compounds with ammonium nitrate vary with the change in composition of the system in an almost rectilinear manner. The graph in Fig. 69 shows how the rate of detonation depends on the composition of mixtures of tetryl or picric acid with ammonium nitrate. T. Urbanski et al. [48] also obtained a rectilinear relationship for nitrostarch mixtures with ammonium or sodium nitrate (Fig. 71, p. 265). 

In military ammonium nitrate explosives containing aluminium even those in which the oxygen balance is negative, the main reaction is assumed to be that of oxidation of the aluminium by reaction with ammonium nitrate ... 

Typical propellants with ammonium nitrate as oxidizer... 

Fig. 126. Thermal layer model of combustion of solid composite propellant with ammonium nitrate, according to Chaiken [2] R—redox reaction flame zone (temperature 7f), u—gas velocity, S—thickness of the thermal layer, T —surface temperature of oxidizer particle, ro—radius of oxidizer particle.

Reactions which formally can be classified as cycloadditions or retrocycloadditions have been observed in homogeneous solution with single electron oxidative initiation, so the observation of parallel activity on irradiated semiconductor suspensions is certainly reasonable. The first example of such a reaction involved the photocatalysis by ZnO or CdS of the ring-opening of a strained hydrocarbon which could also be opened in the dark by a single electron oxidant, ceric ammonium nitrate, Eq. (38)... 

Moderate fire hazard in form of dust. Reacts violently with ammonium nitrate, hydrogen peroxide, lithium, nitrous oxide, potassium chlorate, and sulfur dioxide.2... 

Oxidation of 1-(4-methoxyphenyl)-2-( -substituted phenyl) et hands, 6, by Cerium(IV). Dehydration prevented the oxidative-cleavage study of l-(4-hydroxyphenyl)-2-(4,-substituted phenyl)ethanols, 4, (8). As an alternative study, the oxidation of these phenolic compounds using the homolytic oxidant ceric ammonium nitrate (CAN) in an acidic environment was initiated. However, preliminary oxidations of these compounds were unsuccessful due to the apparent formation of complexes of cerium(IV) with the phenolic hydroxyl groups. 

A-Nitro and acetyl-substituted 1,3,5,7-tetrazocanes are important compounds as explosives and propellants <1996CHEG-II(9)705>. In the syntheses of the nitro-substituted 1,3,5,7-tetrazocanes, their processing, and application, it is possible that they come into contact with ammonium nitrate, or they are directly mixed with this oxidant. Thermal reactivity of the nitro-substituted 1,3,5,7-tetrazocanes has been examined by means of nonisothermal differential thermal analysis <2005MI11>. It has been established that impurities of ammonium nitrate can destabilize some A-substituted 1,3,5,7-tetrazocanes and that this effect is due to acidolytic attack of nitric acid. 

It is therefore a high explosive, although very insensidve to impact and difficult to detonate. In the pure state, it requires a combinadon of an inidator and a high explosive. It is a reladvely safe high explosive, which, however, must be stored in a cool, ventilated place away from acute fire hazards and easily oxidized materials. Ammonium nitrate must not be confined because, if a fire should start, confinement can cause detonadon with extremely violent results. 

Oxidation with ammonium cerium nitrate has to be done in 100% acetic acid (equation 165). In 50% acetic acid, carbonyl compounds are... 

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