Kinetics of reactions involving CN emission. I. General features of reactions with active nitrogen and atomic oxygen

Abstract

Emission of the CN red (A $\rightarrow$ X) and violet (B $\rightarrow$ X) systems accompanying the reactions of active nitrogen with cyanogen, hydrogen cyanide, cyanogen chloride and methylene chloride and of oxygen atoms with cyanogen have been investigated. Bayes's classification of the red emission into the vibrational distributions P$_1$ ($v' \leqslant$ 3) and P$_2$ ($v'$ $\geqslant$ 3) can be extended to the violet system, emission from levels 15 $\geqslant v' \geqslant$ 5 accompanying the P$_1$ distribution and emission from level $v'$ = 0 occurring with the P$_2$ emission. It is shown that the P$_1$ distribution and the excitation of the high vibrational levels of the violet system are due to collisions of CN with energetic species or CN acting as a third body for atomic recombination. The P$_2$ distribution is associated with the formation of electronically excited CN in exothermic transfer reactions such as $N + CH = NC + H.$ $N + CCl = NC + Cl.$