Nitrate oxides

Another matter of concern in pyrotechnic formulations is the possibiHty of exchange reactions occurring between components. Addition of ammonium salts to compositions containing nitrate oxidizers can produce ammonium nitrate, a very hygroscopic material. The composition then becomes quite prone to pick up water and its performance deteriorates. The addition of an ammonium salt to a chlorate-based formulation can lead to the... 

Silver compounds, available from commercial suppHers, are expensive. Reagent grades of sHver(I) carbonate, cyanide, diethjldithiocarbamate, iodate, nitrate, oxide, phosphate, and sulfate are available. Standardized solutions of silver nitrate are also available for analytical uses. Purified grades of sHver(I) acetate, bromide, cyanide, and iodide can be purchased silver nitrate is also made as a USP XX grade for medicinal uses (6). 

Cobalt compounds can be classified as relatively nontoxic (33). There have been few health problems associated with workplace exposure to cobalt. The primary workplace problems from cobalt exposure are fibrosis, also known as hard metal disease (34,35), asthma, and dermatitis (36). Finely powdered cobalt can cause siUcosis. There is Htfle evidence to suggest that cobalt is a carcinogen in animals and no epidemiological evidence of carcinogenesis in humans. The LD q (rat) for cobalt powder is 1500 mg/kg. The oral LD q (rat) for cobalt(II) acetate, chloride, nitrate, oxide, and sulfate are 194, 133, 198, 1700, 5000, and 279 mg/kg, respectively the intraperitoneal LD q (rat) for cobalt(III) oxide is 5000 mg/kg (37). 

The most recent major expln in a US TNT plant occurred in May 1974 at the Radford Army Ammunition Plant. The accident completely destroyed one of the three continuous nitration lines at the plant. According to the AMC News, Sept 1974, the investigation board reported that an operator inadvertently introduced a 5 to 6-foot rubber hose to clean out unwanted material that had collected in a transfer line leading to the nitrator, when the hose was pulled from his hands into the nitrator. This resulted in a rapid temp rise and subsequent explosion. The hose was commonly used in this manner . The material causing the blockage in the transfer line was believed to be an oxidation product of TNT, 2,2 -dicarboxy-3,3, 5,5,-tetra-nitroazoxybenzene, also referred to as White Compound. The introduction of the rubber hose caused a rapid, exothermic oxidation reaction between the hose material and the mixed acid present. The heat generated by this reaction caused a local acceleration of the normal nitration/oxidation reactions which occur in the nitrator until a critical temp was reached, at which point rapid oxidation of DNT/TNT proceeded as a runaway reaction, igniting the material present in the vessel. 

H2S04 axis corresponds to nitration to a N content of more than 12.75% N. In the area limited by AA-BB and A arespectively, the products contain 11.1-12.75% N. Between BB-CC and b B— C C respectively, products of 9.15— 11.1% N are obtd. To the left of the line CC lies an area corresponding to nitrating acids that give non-homogeneous, low-grade nitrated, oxidized or hydrolyzed products. The outlines of the curves AA, BB, CC, resemble those for NC and also those for nitronium ion N02+ concns... 

In addition to nitration, oxidation of the S atom also takes place, resulting in the formation of the sulphoxide (Ref 5). It was used in Ger during WWII as a component of a non-fusible expl compn known under the name of Pressling (qv) (Refs 2 4)... 

Liquid-liquid reactions (nitrations, oxidations or hydroxylations using H2O2, brominations, iodinations) 1-5 50-250 250 500... 

E8. Endo, S Inada, K., Nakae, H., Arakawa, N Takakuwa, T., Yamada, Y., Shimamura, T., Suzuki, M., Taniguchi, S and Yoshida, M., Nitrite/nitrate oxide (NOc) and cytokine levels in patients with septic shock. Res. Commun. Mol. Pathol. Pharmacol. 91,347-356 (1996). 

Many metal oxo-compounds (nitrates, oxides and particularly sulfates) and sulfides are reduced violently or explosively (i.e. undergo thermite reaction) on heating an intimate mixture with aluminium powder to a suitably high temperature to initiate the reaction. Contact of massive aluminium with molten salts may give explosions [1], Application of sodium carbonate to molten (red hot) aluminium caused an explosion [2]. 

When dry, the oxygen-balanced salt explodes readily on percussion, grinding or heating to 105°C. This instability is attributed to presence of impurities (nitrate, oxide, or basic oxalate) in the product [1]. It is so thermally unstable that storage is inadvisable [2],... 

An explosion in flour-bleaching operations was attributed to violent decomposition of the basic nitrate [1], which is an impact-, friction- and heat-sensitive explosive [2]. The instability is associated with the presence of reducant and oxidant functions in the same molecule. The previous formulation as tin(II) nitrate oxide is revised to that above. 

See Other MERCURY COMPOUNDS, METAL NITRATES, OXIDANTS... 

Cambella and Antia [385] determined phosphonates in seawater by fractionation of the total phosphorus. The seawater sample was divided into two aliquots. The first was analysed for total phosphorus by the nitrate oxidation method capable of breaking down phosphonates, phosphate esters, nucleotides, and polyphosphates. The second aliquot was added to a suspension of bacterial (Escherichia coli) alkaline phosphatase enzyme, incubated for 2h at 37 °C and subjected to hot acid hydrolysis for 1 h. The resultant hot acid-enzyme sample was assayed for molybdate reactive phosphate which was estimated as the sum of enzyme hydrolysable phosphate and acid hydrolysable... 

Cobalt Copper Acetylene, hydrazinium nitrate, oxidants Acetylene and alkynes, ammonium nitrate, azides, bromates, chlorates, iodates, chlorine, ethylene oxide, fluorine, peroxides, hydrogen sulfide, hydrazinium nitrate... 

Alkyl nitrates Oxidation capacity Photochemistry -30 Gg Significant... 

The stepwise nature of nitrification during the aerobic decomposition of detrital PON is illustrated in Figure 24.6. Initially, the degradation of PON produces ammonium, which stimulates the growth of the nitrate oxidizers. These bacteria transform the ammonium into nitrite, causing ammonium concentrations to decline and nitrite concentrations to rise. The elevated nitrite levels stimulate the growth of the nitrite oxidizers. These bacteria transform the nitrite into nitrate. Eventually all of the DIN is oxidized to nitrate. The residual pool of PON includes microbial biomass and any PON too inert to be degraded by aerobic marine bacteria. 

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. 

Hexanitroazobenzene (HNAB) (90) can be synthesized from the nitration-oxidation of 2,2, 4,4 -tetranitrohydrazobenzene (102) with mixed acid, the latter synthesized from the reaction of aqueous hydrazine with 2,4-dinitrochlorobenzene (95) in the presence of an inorganic carbonate. " ... 

Dinitrochlorobenzene (95) reacts with pyridine to form 2,4-dinitrophenylpyridinium chloride (103), a reactive intermediate which readily reacts with a variety of nucleophiles. The reaction of (103) with hydrogen sulfide yields 2,2, 4,4 -tetranitrodiphenylsulfide (104), which on nitration-oxidation with fuming nitric acid, yields 2,2, 4,4, 6,6 -hexanitrodiphenylsulfoxide (105). The sulfide (104) is also formed from the reaction of two equivalents of 2,4-dinitrochlorobenzene (95) with sodium thiosulfate or sodium disulfide in aqueous ethanol. ... 

The conjugation in 2,2, 4,4, 6,6 -hexanitroazobenzene (HNAB) (90) is also reflected in its thermal stability (m.p. 220 °C). The synthesis of HNAB from picryl chloride and 2,4-dinitrochlorobenzene is discussed in Sections 4.8.1.2 and 4.8.1.3 respectively. 3,3, 5,5 -Tetraamino-2,2, 4,4, 6,6 -hexanitroazobenzene (149) has been synthesized by an unusual but efficient route which involves the nitration-oxidative coupling of 3,5-dichloroaniline (147) on treatment with nitric acid, followed by reaction of the resulting product, 3,3, 5,5 -tetrachloro-2,2, 4,4, 6,6 -hexanitroazobenzene (148), with ammonia. Both the tetrachloro (148) and tetraamino (149) derivatives exhibit high thermal stability. 

Agrawal and co-workers have reported the synthesis of A,A -bis(l,2,4-triazol-3-yl)-4,4 -diamino-2,2, 3,3, 5,5, 6,6 -octanitroazobenzene (17) (BTDAONAB) via nitration-oxidative coupling of 4-chloro-3,5-dinitroaniline (152) followed by nucleophilic displacement of the chloro groups with 3-amino-1,2,4-triazole. BTDAONAB has the unique distinction of being the most thermally stable explosive reported so far (DTA exotherm 550 °C) as compared to well known thermally stable explosives such as TATB ( 360 °C), TACOT ( 410 °C), NONA ( 440 50 °C), and PYX ( 460 °C). 

Tetryl (8) can be prepared from the nitration-oxidation of A, A-dimethylaniline (90) with a variety of nitrating agents and conditions, including the use of a large excess of 70 % nitric... 

TABLE 4.2 Burning Rates of Binary Mixtures of Nitrate Oxidizers with Magnesium Metal... 

Barium nitrate oxidizer, Ba(NO 3) 2 Potassium nitrate oxidizer, KNO3... 

Compositions made with aluminum tend to be quite stable. However, moisture must be excluded if the mixture also contains a nitrate oxidizer. Otherwise, a reaction of the type... 

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