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Chemical Kinetics of the Thermal Decomposition of NTO
Author(s) -
Kondrikov Boris N.,
Smirnov S. P.,
Minakin A. V.,
Doherty Ruth M.
Publication year - 2004
Publication title -
propellants, explosives, pyrotechnics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.56
H-Index - 65
eISSN - 1521-4087
pISSN - 0721-3115
DOI - 10.1002/prep.200400027
Subject(s) - autocatalysis , thermal decomposition , decomposition , arrhenius equation , chemical decomposition , chemistry , reaction rate constant , kinetics , order of reaction , thermodynamics , chemical kinetics , activation energy , materials science , organic chemistry , catalysis , physics , quantum mechanics
The kinetics of thermal decomposition of 3‐nitro‐2,4‐dihydro‐3H‐1,2,4‐triazol‐5‐one (NTO) in the temperature interval from 200 °C to 260 °C was investigated using a glass Bourdon gauge. The overall decomposition reaction includes two distinct stages: the fast first‐order decomposition and the subsequent autocatalytic reaction. The importance of the first stage increases with increasing decomposition temperature and decreasing loading density of the Bourdon gauge ( m/V). A period of preliminary heating, at a lower temperature, strongly influences the autocatalytic stage when the decomposition is carried out at a higher temperature. In the temperature domain 200–220 °C, the Arrhenius constants of the decomposition reaction are found to be close to the values usually observed for nitrocompounds: E =173 kJ/mol and log 10 k ≈12.5 (s −1 ). It is shown that a simple model of NTO decomposition based on an autocatalytic reaction of the m ‐th order can describe the course of the decomposition at high temperature but the m number appears to be excessively high, up to 4. A new model of the decomposition is developed, including an initial monomolecular reaction, decomposition of the crystalline substance, and an autocatalytic reaction of NTO dissolved in liquid decomposition products. This model gives the common order of autocatalysis, m =1.