THE KINETIC-PARAMETERS OF THE PRIMARY STAGE OF THERMAL-DECOMPOSITION OF ORGANIC NITRATES

The experimental data concerning the initial stage of nitroester decom position is considered. The primary reaction is the homolytic abstract ion of NO2, whose activation energy (160 - 170 kJ/mol) is virtually in dependent of the structure and state of aggregation of a substance. Th e difference in the rates of decomposition of various nitrates may lar gely be attributed to variations in the activation energy. The depende nce of the rate of decomposition on the nitrate structure is satisfact orily described by the Taft equation. The relationship between the rat e of decomposition and the frequency of stretching vibrations of the O -NO2 bond is established: the lower the frequency, the faster nitroest er decomposition occurs. The possibility of parallel routes of the ini tial conversion via elimination of HNO3 and HNO2 is discussed.