Kinetics of heat release during the reaction of n-decane with nitrogen dioxide in the liquid phase

The rates of heat release in the nitrogen dioxide-n-decane system at a molar ratio of nitrogen oxides to n-decane (beta) from 2.4 . 10(-3) to 3.1 and gaseous volumes per mole of n-decane (V(g)) equal to 0.05-4.5 were studied in the 55.2-92.8 degrees C temperature range. The initial rate of the process is determined by the interaction of NO2 with n-decane. The equilibrium constants of dissociation of N2O4 in n-decane and Henry's constants of NO2 and N2O4 in an n-decane solution were determined by complex analysis of the thermodynamic equilibrium in the NO2-n-decane system and dependences of the initial rates an V(g) and beta. The experimentally observed self-acceleration of the process in the region of high beta and low T values vias suggested to be doe to the reaction of N2O4 with intermediate oxidation products. The rate constants of the reaction of NO2 with n-decane were compared with analogous values determined in its mixtures with HNO3 solutions.