Infrared chemiluminescence from a flow reactor has been used to study the H þ CH 2 XI and N þ CH 2 X (X ¼ Cl, F, I, H) reactions at 300 K. Both the HI þ CH 2 Cl and HCl þ CH 2 I channels were identified for the H þ CH 2 ClI reaction. The HCl channel involves adduct, HICH 2 Cl, formation as confirmed by the D þ CH 2 ClI reaction, which gave both HCl and DCl products. The nascent HCl(v) distribution from the H þ CH 2 ClI reaction was P 1-P 5 ¼ 25 : 29 : 26 : 13 : 7. The rate constant for the HCl(v) formation channel is estimated to be 4 times smaller than that for the H þ Cl 2 reaction. The highest HCl(v) level observed from the H þ CH 2 ClI reaction implies that the C-Cl bond energy is 50.2 kJ mol À1 lower than that of the Cl-CH 3 bond, which is in modest agreement with recent theoretical estimates. The H þ CH 2 FI reaction gave a HF(v) distribution of P 1-P 3 ¼ 77 : 15 : 8. The C-F bond energy in CH 2 FI is estimated to be 4 460.2 kJ mol À1 , based on the highest HF(v) level observed, the upper bound being the same as that of F-CH 3. When N atoms are added to the flow reactor, the HCl(v) emission intensities from H þ CH 2 ClI increased by up to 2-fold, which is attributed to the N þ CH 2 Cl ! HCl þ HCN reaction. Concomitant weak emission from HCN and HNC could also be observed; however, the main product channel is thought to be NCH 2 þ Cl. Strong visible CN(A-X) emission was also observed when H=N=CH 2 XI were present in the reactor. If the CH 2 X radicals were produced by the F þ CH 3 X reaction in the presence of N atoms, similar results were obtained. The N þ CH 2 N reaction is proposed as the first step that leads to CN(A) formation with NCN as an intermediate.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.