DETERMINATION OF RATE CONSTANTS OF REACTIONS OF N3 AND NC1 FREE-RADICALS USING A SIMULATION TECHNIQUE

A numerical integration method was used to solve the mathematical system corresponding to the mechanism of the reaction of Cl atoms with chlorine azide, N3Cl. The identification of calculated kinetic curves of the species involved in the mechanism with the experimental curves led to the determination of rate constants of the following secondary reactions: (2)Cl + N3 → NCl + N2(3)N3 + N3 → 3N2(4)NCl + NCl → N2 + Cl2. At 298K, the rate constants were found to be k2: 0.75 - 1.5 × 10-11, k3: 5 - 8 × 10-11, and k4: 0.5 - 1 × 10-11 (units are cm3 molecule-1 sec-1). © 1979.