Infrared chemiluminescence studies of the reactions H + PCl₃, H + VOCl₃, and H + CrO₂Cl₂

Abstract

We report the study of the three title reactions in a flowing afterglow apparatus using the method of IR‐chemiluminescence. HCl emission was observed from excited vibrational states in each case and attributed to the reactions. H + PCl3 → HCl(v' ≤ 5) + PCl2. H + VOCl3 → HCl(v' ≤ 4) + VOCl2. H + CrO2Cl2 → HCl(v' ≤ 4) + CrO2Cl. H + PCl33 yields a bell shaped vibrational distribution (N1: N2: N3: N4: N5 = 0.11: 0.24: 0.38: 0.17: 0.10) indicating a direct mechanism. The HCl product distribution for the two other reactions can be described by vibrational temperatures of 3890 ± 250 K (H + VOCl3) and of 4400 ± 350 K (H + CrO2Cl2). It is concluded that the chlorine abstractions H + VOCl3 and H + CrO2Cl2 proceed via formation of long lived complexes.