O. P. Korobeinichev

Investigation of rapid processes in the thermal decomposition of ammonium perchlorate with a transit time mass spectrometer

1. The composition of the gas phase during the thermal decomposition of pure ammonium perchlorate and ammonium perchlorate with an addition of 5% Fe2O3 at 400° and a pressure of 10–200 mm was investigated with a transit time mass spectrometer and by a procedure permitting recording of active particles and aggressive gases. 2. A change in the composition of the gas phase during the reaction and an influence of the additive on the composition of the decomposition products were detected, which is explained by the role of the additive as a catalyst of reactions in the gas phase.

Mass spectrometric investigation of the kinetics and mechanism of the gas phase and heterogeneous catalytic decomposition of perchloric acid in mixtures of hydrogen, methane, and ammonia

1. The kinetics of the reaction of perchloric acid in the presence of hydrogen, methane, and ammonia on the catalyst Fe2O3 at 320–380° and without a catalyst in a Pyrex reactor at 450–550° was investigated by a mass spectrometric method. The Influence of the ratio of the surface of the reactor to its volume (S/V) on the rate of decomposition of HClO4, pure and in mixtures of fuels — without a catalyst — was investigated. 2. Hydrogen increases the rate of gas phase decomposition of HClO4 to a greater degree, the larger PH2/PHClO4. The reaction is first order with respect to hydrogen and acid. Methane and ammonia do not have any appreciable influence on the rate of the gas phase decomposition of HClO4. The reaction is first order with respect to the acid and zero order with respect to the fuel. 3. In the heterogeneous catalytic decomposition of HClO4 on Fe2O3, methane has no appreciable influence, but H2 approximately doubles the rate of decomposition of HClO4 at 320°.

Study of the kinetics and mechanism of the sublimation of ammonium perchlorate by mass-spectrometric thermal analysis

The mass-spectrometric thermal analysis method was used to study the kinetics of the sublimation of ammonium perchlorate. The obtained data make it possible to express a theory regarding the reasons for the divergence of the kinetic constants of sublimation in vacuo, obtained by different investigators.

Mass spectrometric investigation of the catalysis of secondary processes of decomposition of ammonium perchlorate

1. Data were obtained on the mechanism of the primary and secondary steps of the heterogeneous catalytic decomposition of perchloric acid. A substantial increase in the rate of the catalytic decomposition of perchloric acid in the presence of ammonia was detected. 2. The activities and the activity series of the catalysts were determined; they coincided with the activity series of the same catalysts for the thermal decomposition of ammonium perchlorate (APC), which confirms the conclusion of a determining role of the breakdown of perchloric acid in the decomposition of APC.