Thermal reactivities of I I commercial explosives with different nitric ester contents, oxidizing systems of 10 classical emulsion explosives (water in oil (W/O) type), four of these fortified by 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) or pentaerythritol tetranitrate (PETN), and three samples of W/O emulsion explosives were examined by means of differential thermal analysis (DTA) and data were analyzed according to the Kissinger method. The reactivities, expressed as the E-a R-1 slopes of the Kissinger relationship, correlate with the squares of the detonation rates of the corresponding explosive mixtures in the form of the modified Evans-Polanyi-Semenov ( E-P-S) equation. In explosive mixtures, the thermal reactivity of the oxidizing system and/or its mixture with a high explosive replaces the primary thermal reactivity of explosophore groups in the individual energetic materials. Addition of any inorganic nitrate to ammonium nitrate in a classical W/O, emulsion explosive was found to result in a decrease in the detonation parameters of the resulting mixture.