Kinetics and mechanism of the branched chain decomposition of nitrogen trichloride in the gas phase and chemical oscillations in this process

Numerical simulations of the oscillating regimes of the nitrogen trichloride self-ignition in a closed volume are carried out using a one-dimensional system of ordinary differential equations (ODE). It is shown that the suggested mechanism agrees with the experimental data. To find a solution that allows oscillations, it is sufficient to take into account (a) NC13 adsorption and desorption on reactor walls, (b) nonlinear chain termination $$Cl^ \bullet + Cl_2 ^3 \Pi _{ou}^ + \to Cl^ \bullet + Cl_2 ^1 \Sigma _g^ - $$ , and (c) energetic chain branching $$Cl_2 ^3 \Pi _{ou}^ + + NCl_3 - NCl_2 + Cl^ \bullet + Cl_2 ^1 \Sigma _g^ - $$ . The assumption that NC13 desorption from the reactor surface takes place during oscillations and changes the properties of the reactor surface leads to oscillation regimes in simulation, which agrees qualitatively with the experiment.