Guanidine perchlorate

Marckwald [29] proposed the use of guanidine perchlorate in explosives. It has the important advantages of being stable, non-hygroscopic and moderately sensitive to shock, and is capable of producing a violent explosion. Its preparation, by fusing dicyandiamide with ammonium perchlorate at 150-160°C, offers no significant difficulties. 

Guanidine perchlorate heated to a temperature above 300°C undergoes explosive decomposition. Glasner and Makovky [13] studied the thermal decomposition of guanidine perchlorate, and concluded that the composition can be expressed by the following equations  

in the first stage of reaction, ammonium perchlorate and cyanamide are produced. The latter furnishes melamine, which is decomposed in turn under the influence of ammonium perchlorate or the perchloric acid that is produced from the perchlorate. 

The activation energy of the decomposition of guanidine perchlorate within the temperature range 390-440°C, quoted in the same contribution, is E = 30.5 kcal/mole. The decomposition is catalysed by metallic oxides such as Fe203, CuO and V205, and by platinum. 

As for its explosive strength, guanidine perchlorate is similar to tetryl. Its sensitiveness to shock is comparable with that of picric acid. The rate of detonation is 6000 m/sec at a density of 1.15 and the net expansion in the lead block test is about 400 cm3. 

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Preparation and explosive properties of guanidine perchlorate) 6) Anon, Jahresber-Chem-TechnReichsanstalr 6, 93(1927)... 

Khim 10(1), 454-7(1965) Sc CA 62, 12515 (l9659(Enthalpy of formation of guanidine perchlorate, nitrate, and sulfate) (Give the value —287kcaljn)... 

Others, for instance guanidine perchlorate, pyridine perchlorate, are among the strongest explosives. 

Dicyandiamidine perchlorate [30] is an appreciably weaker explosive than guanidine perchlorate, hence it is of no practical importance. 

Guanidine perchlorate is relatively stable to heat and to mechanical shock but possesses extraordinary explosive power and sensitivity to initiation. Naoum46 states that it gives a lead block expansion of about 400 cc. and has a velocity of detonation of about 6000 meters per second at a density of loading of 1.15. 

Reacts to form explosive products with alkanes + oxygen (forms peroxides), cyano-guanidine, perchloric acid (forms fluorine perchlorate gas), potassium chlorate (forms fluorine perchlorate gas), potassium hydroxide (forms potassium trioxide). 

Buffering in an aprotic medium is sometimes a problem. Proton donors, such as a suitable phenol, malonic ester, or amine salt, together with the corresponding base, may be an acceptable solution. Guanidine perchlorate [472] has been proposed as an efficient proton donor (and supporting electrolyte) in aprotic solvents, as it brings the protons into the Helmholtz double layer. 

Salts of hydrazine perchlorate and chlorate complexes Nitrosyl perchlorate Hydroxylaminc perchlorate Methylaminc perchlorate Guanidine perchlorate Nitroguanidine perchlorate Ruoroammonium perchlorate Nitronium perchlorate Perchloric acid and chlorine oxides Perchloric acid... 

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