Kinetic mechanisms in nitrogen + chlorine radical systems. Part 2.—Kinetics of elementary reactions of nitrogen trichloride and of the dichloramino free radical
The use of a photometric method for the measurement of NCl2 radical concentrations is described. The kinetics of the reactions, [graphic ommitted] and [graphic ommitted] were studied; over the range 259-373 K, the rate constants k2 and k3 are given by k2= 10(11.7 ± 0.1) exp [(0 ± 200)/T] cm3 mol–1 s–1, k3= 10(12.6 ± 0.4) exp [(–1550 ± 500)/T] cm3 mol–1 s–1. Kinetic studies on the decomposition at 298 K of NCl3 in the presence of H2 CH4 and C2H6, and atom and radical scavengers (ClNO, Br2) were made. The results showed that one chlorine atom was produced in reaction (2) for every NCl2 radical reacted. The following mechanism for this reaction is suggested; NCl2+ NCl2→ N2Cl3+ Cl, N2Cl3+ M ⇌ N2CI2+ Cl + M. The energies of nitrogen-chlorine bonds are discussed.