Ammonium nitrate thermolysis

The increase in the rate of decomposition under the influence of added Cr203 and K2Cr207 is shown on Figs. 171 and 172 respectively.lt has been found that an increase of the rate occurred only at temperatures near to the melting point of the samples. Guiochon [17] also found that cobalt salts increase the rate of thermolysis of ammonium nitrate. Other mineral salts (of manganese, nickel and copper) have a similar but much weaker action. A large number of salts of other metals are without any noticeable action. 

Oxidation of these complexes releases the apical carbon atom and its substituent in the form of an organic derivative.2 Thus ceric ammonium nitrate oxidation of an RCCo3(CO)9 complex produces the carboxylic acid, RC02H, when the reaction is carried out in aqueous acetone. Thermolysis of RCCo3(CO)9 produces acetylenes or acetylene hexacarbonyl dicobalt complexes, depending on the reaction conditions. Useful applications of these cluster complexes in organic synthesis remain to be developed. 

Reaction of 6 (3-hydroxy-steroids with ceric ammonium nitrate was reported to give the 6(3, 19-epoxides,123 and fragmentation of 5- and 19-hydroxy-compounds were also reported. A detailed investigation of the hypoiodite reaction and the related Pb(OAc)4 oxidation of a 5a-bromo-6(3-hydroxy-compound indicated that for the former a halocarbon solvent promotes 6(3,19-epoxide formation.124 Photolysis of the 17a-iodobenzoate (148) with PhICI2 gave the 9 -chloro-derivative (149) which on thermolysis gave a good yield of the 9(11), 16-diene (150).125 Photolysis of... 

Activated primary nitro compoimds, i.e., those bearing an electron withdrawing group (EWG) geminal to the nitro group (i.e., 13 R = EWG), usually undergo dehydration reaction with acids [90] or under acylation conditions [86] or on thermolysis [91]. Some activated nitro compoimds have also been reported to imdergo dehydration to nitrile oxides 5 on treatment with Ce(III) ammonium nitrate [92] and thionyl chloride [93]. 

Energetic Materials 31. Fast Thermolysis of Ammonium Nitrate, Ethylenediammonium Dinitrate and Hydrazinium Nitrate and the Relationship to the Burning Rate Combustion and Flame 76, 393-401. 

Several ammonium nitrate salts without alkyl groups have been studied by fast thermolysis. These are ammonium nitrate [77], triaminoguanidinium nitrate (TAGN) [78], hydroxylammonium nitrate (HAN) [79], and hydrazinium nitrate [77]. HNO3 is the initially detected gas product in all cases. All but HAN produce NH3. HAN is conspicuous and unusual because of the... 

---