Valery P. Sinditskii, Ludmila Ya. Melnikova, Anastasia D. Smirnova, Nikolay V. Yudin, Alexei A. Konnov, Igor L. Dalinger, Michael S. Klenov
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Thermal Decomposition Kinetics and Decomposition Mechanism of (Dinitropyrazolyl)Azoxyfurazanes
The decomposition of azoxy derivatives of dinitropyrazole and furazan, the first example in which an azoxy group is coupled to a pyrazole ring nitrogen, has been studied in detail using DSC, TGA, isothermal TGA, and manometry methods. The studies showed that the degradation of azoxy compounds starts with the cleavage of the bond between the N(O) atom of the azoxy group and the furazan cycle. It was found that under conditions of decomposition product removal, this stage can occur without heat release or with heat release without a pronounced peak. The insignificant heat effect of the initial decomposition stage of azoxy compounds makes it difficult to determine the true kinetic parameters using the standard DSC method, as the observed heat effect is actually due to the decomposition of intermediates. At the same time, decomposition under closed conditions can increase the decomposition rate constants by a factor of 10 or more. A possible mechanism for the decomposition of azoxy compounds has been proposed based on the kinetic data obtained and the analysis of the decomposition products.
期刊介绍:
As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.