KINETIC COMPENSATION EFFECT AND THERMOLYSIS MECHANISMS OF ORGANIC POLYNITROSO AND POLYNITRO COMPOUNDS

The present study starts from the published values of the Arrhenius pa rameters E-a and log A of thermolysis in the condensed state of seven nitrosamines and one hundred organic polynitro compounds. On the basis of the linear relationship between E-a log A, the set studied has bee n divided into several reaction series, each of which is characterized by a mechanism of primary thermolysis. For compounds with intense int ermolecular interactions in a crystal, the classification mentioned is codetermined by the stabilizing effect of the crystal lattice. In the context of this effect, the absence of an effect of solid-liquid tran sition on thermal reactivity of octogen (HMX) has been confirmed. The idea also presented is that, in the primary homolysis in thermolyses o f polynitro compounds, there takes place a mutual interaction of molec ules of the given compound, which is analogous to termination interact ions of nitroarenes in radical polymerizations. (C) 1997 Elsevier Scie nce B.V.