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Infrared chemiluminescence from a flow reactor has been used to study the H þ CH2XI and N þ CH2 X( X¼ Cl, F, I, H) reactions at 300 K. Both the HI þ CH2Cl and HCl þ CH2I channels were identified for the H þ CH2ClI reaction. The HCl channel involves adduct, HICH2Cl, formation as confirmed by the D þ CH2ClI reaction, which gave both HCl and DCl products. The nascent HCl(v) distribution from the H þ CH2ClI reaction was P1-P5 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 Cl2 reaction. The highest HCl(v) level observed from the H þ CH2ClI reaction implies that the C-Cl bond energy is 50.2 kJ mol 1 lower than that of the Cl-CH3 bond, which is in modest agreement with recent theoretical estimates. The H þ CH2FI reaction gave a HF(v) distribution of P1-P3 ¼ 77 : 15 : 8. The C-F bond energy in CH2FI is estimated to be 4 460.2 kJ mol  1 , based on the highest HF(v) level observed, the upper bound being the same as that of F-CH3 . When N atoms are added to the flow reactor, the HCl(v) emission intensities from H þ CH2ClI increased by up to 2-fold, which is attributed to the N þ CH2Cl ! HCl þ HCN reaction. Concomitant weak emission from HCN and HNC could also be observed; however, the main product channel is thought to be NCH2 þ Cl. Strong visible CN(A-X) emission was also observed when H=N=CH2XI were present in the reactor. If the CH2X radicals were produced by the F þ CH3X reaction in the presence of N atoms, similar results were obtained. The N þ CH2N reaction is proposed as the first step that leads to CN(A) formation with NCN as an intermediate.

Infrared chemiluminescence: Evidence for adduct formation in the H + CH2XI reaction and studies of the N + CH2X (X = Cl/F/I/H) reactions