Tetryl decomposition

Ditetryl is more sensitive to impact than tetryl (it is exploded by a 2 kg weight falling 21-26 cm as compared with 49-51 cm for tetryl). Its ignition temperature is 214°C (that of tetryl is 196°C). It is much less stable than tetryl decomposition occurred on heating at 95°C for 4 days (tetryl withstands 185 days heating [66]). 

Table 8-32. Composition of Gaseous Products of Tetryl Decomposition...

These are products extracted out of soil contaminated with TNT, RDX, and TETRYL (Trimtrophcnyl-M-mcthyInitramine). For TNT a decomposition product that had a longer half-life in the soil was 4-amino-dinitrotoluene, so in doing area reduction one should include this product. 

Kinetics of isothermal decompn of K perchlorate) 3) Inst of Study of Rate Processes, Univ of Utah, "The Isothermal Decomposition of Tetryl and Hydrazine Nitrate , TechRept No XL111 (Dec 1954) Contract N7-onr-45107 4) R.M. 

Cook (Ref 1), in describing thermal decomposition of some HE s conducted in the quartz spring apparatus (described in Ref 1, p 175 and shown there in Figs 8.1a 8.1b), stated that PETN, RDX, Tetryl and to a small extent TNT decomposed autocatalyti-cally. EDNA followed the first-order decomposition law only until about 5% of the explosive had decomposed and then the reaction stabilized. The term autostabilization was applied here on the supposition that one of the condensed decomposition products of EDNA which accumulated in the explosive apparently tended to stabilize the bulk of expl and thus slow down the decomposition. After about 10% of the expl had decompd, however, the "autocatalysis developed. 

If decomposition proceeds at the same rate over entire range until practically no sample remains (like with(AN),it is said that the explosive exhibits (ideal) first-order decomposition, and that no autocatalyzation takes place as in the decompn of.PETN,Tetryl or RDX. EDNA followed the first-order decomposition law only until ca 5% of the expl had decomposed. This was followed by autostabilization, the term applied here on the supposition that one of the condensed decompn products of EDNA which accumulated in the sample apparently tended to stabilize it, thus slowing down the decompn. After ca 10% of the expl had decomposed, however, autocatalysis developed... 

Tests lasting for many years have shown that 20 years of storage, at room temperature involve no discemable changes in tetryl, nor was any distinct decomposition of tetryl observed at 65°C after 12 months at 75°C after 6 months and at 100°C after 100 hr. 

According to Farmer [32] the activation energy of the thermal decomposition of tetryl =60.0 keal and log 5=27.5. Hinshelwood [38] reports similar values. A. J. B. Robertson [41] found, however, that at higher temperatures (211-260°Q =38.0 kcal and log 5=15.4. According to Szyc-Lewanska [42] at still higher temperatures (260-300°C) the activation energy is even lower, viz. E= approximately 20.0 kcal (based on the data given above [40]). 

Roginskii and Lukin [43] found that tetryl is not liable to explode when heated at 150°C in a sealed ampoule, though at temperatures above 150°C, e.g. between 150 and 170°C, explosion may ensue as result of chain reactions occurring during decomposition on long-continued heating. 

The explosive decomposition of tetryl, like that of other explosives, depends on the method of initiation, density etc. Haid and Schmidt [45] give the following equation for the decomposition of tetryl, at a density of 1.56 ... 

For every 10 °C increase in temperature, the rate of decomposition is approximately doubled, but may increase as much as 50 times if the explosive is in the molten state. The rates of decomposition depend on the condition of storage and the presence of impurities which may act as catalysts. For example, nitroglycerine and nitrocellulose decompose at an accelerated rate due to autocatalysis, whereas the decomposition rate of TNT, picric acid and tetryl can be reduced by removing the impurities which are usually less stable than the explosive itself. With many of the explosives the presence of moisture increases the rate of decomposition. 

In addition to the ability of certain substances to combine with the products of the decomposition of nitrocellulose, it is possible that the same or other substances may have a positive or a negative catalytic effect and may hasten or retard the decomposition by their presence. But it has not yet been made clear what types of chemical substance hasten the decomposition or why they do so. Nitrogen dioxide hastens it. Pyridine hastens it, and a powder containing 2 or 3% of pyridine will inflame spontaneously if heated for half an hour at 110°. Powders containing tetryl are very unstable, while those containing 10% of trinitronaphthalene (which does- not react with the products of decomposition) are as... 

The same reaction occurs at lower temperatures 0.665% of a given portion of the material decomposes in 3 years at 20°, 2.43% in 1 year at 35°, 0.65% in 10 days at 50°, and 100% during 14 hours heating at 100°. The decomposition is not self-catalyzed. The product, hexanitrosobenzene, m.p. 159°, is stable, not hygroscopic, not a primary explosive, and is comparable to tetryl in its explosive properties. 

Fig 2 Kinetic gas-evolution curves in the decomposition of Tetryl with the addition of Picric Acid at 150° 1) Tetryl alone 2) 0.62 mole of Picric Acid per mole of Tetryl 3) 1.26 moles of Picric Acid per mole of Tetryl 4) 2,57 moles of Picric Acid per mole of Tetryl... 

According to Ingraham [19b], tetranitroaniline has shown evidence of decomposition by the heat test at 65.5°C when only a small amount of moisture was pie-sent. The main product of decompositions was II. Prolonged heating at 75°C results in loss of a nitro group. At 120°C decomposition takes place which proceeds in a way similar to that of tetryl. The initiation temperature is 231-233°C. The specific gravity of the product is 1.867 [19],... 

Based on effects observed in water (Navy 1984b), tetryl released to soil is expected to be susceptible to slow hydrolysis in acidic and neutral soils and to relatively rapid hydrolysis in highly alkaline soils (HSDB 1994). Samples of water collected from lysimeters containing tetryl-contaminated soil indicated that the major transformation products were picric acid (5-14%) and other polar, water- soluble decomposition products no tetryl was detected in the water, or in the soil at the end of the study, suggesting complete hydrolysis (Kayser and Burlinson 1988 Navy 1982). The specific reaction leading to these products was not determined. Because tetryl is subject to photolysis in water, it may be susceptible to photolysis on sunlit soil surfaces (HSDB 1994). 

HRGC/MS has been used to identify tetryl in explosive debris (Tamiri and Zitrin 1986). Tetryl was reported to decompose by hydrolysis during the analysis, but its decomposition product, N-methylpicramide, was well defined and served as evidence for the presence of tetryl (Tamiri and Zitrin 1986). The authors of this report concluded that the hydrolysis of tetryl during the GC analysis could take place at the injector, which was held at relatively high temperatures (Tamiri and Zitrin... 

Properties Brownish crystals. Melts with decomposition at 210° and deflagrates at about 226 . Powerful and sensitive high explosive, similar to Tetryl. Detonation rate (d = 1.6) 7500 m/sec. On long storage stability not very satisfactory, particularly in presence of moisture, which tends to promote hydrolysis.37... 

Brisance — no info Decomposition Temperature — 180° with evolution of white fumes Detonation Velocity — 7132m/sec at density 1.35 Heat of Combustion at Cv and 18°— 519kcal/mole Heat of Formation at Cv — 74.6kcal/nole Hygroscopicity — very high Impact Sensitivity with 5kg Weight — at the heights 1.0 to 1.5 meters only 2 detonations out of 100 drops Initiation Sensitivity — detonates very difficultly at density 0.70 by means of 3g MF Power by CUP Method (Modified Trauzl Test) — 69.5% PA vs Tetryl 120% Stability — low... 

Mass spectra of the important explosives RDX, HMX, TNT, TNB and Tetryl were first briefly reported by Meyer (Ref 34) and later investigated in greater detail with high resolution and labeling techniques by Bulusu et al (Ref 45). Mass spectrometric studies of the photodecomposition of labeled dimethyl-nitramine (Ref 56) and the thermal decomposition of HMX and RDX (Refs 27 31) illustrate the application of these techniques to studies of reaction mechanism and bond dissociation processes. Nitroguanidines have only recently been investigated by Beynon (Ref 35)... 

Thermal Decomposition. Betw 80 140° a reversible deamination occurs with the loss of 4 moles of ammonia, and betw 240 280° an irreversible exothermic reaction occurs resulting finally in an expln at ca 280°. A residue of Ni oxide contg some chloride is left (Ref 17) Hydrazine Complex. A complex with the empirical compn Ni(C104)2-Ni(0H)C104.5N2H4.-H2 0 has been reported to be a pale blue solid (Ref 5) with the following expl props Effectiveness as a Detonator. Wts of the subs which will initiate the following expls are Tetryl O.lOg, TNT 0.15g, TNAns 0.45g (Ref 7) Explosion Temperature. 175° (Ref 6)... 

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