Infrared chemiluminescence studies of Cl + HI, HBr, DBr, PH3, PD3, and GeH4: vibrational energy disposal and rate constants

The Cl + HI, HBr, DBr, GeH4, PH3, and PD3 reactions were studied at room temperature with infrared chemiluminescence from a flowing afterglow apparatus. The HCl and DCl vibrational energy distributions and the relative rate constants for Cl + PH3, GeH4 and HI were measured. Since the rate constant for Cl + HI reaction is available in the literature, the relative measurements can be converted to absolute rate constants. The HCl distribution from Cl + HI was nu1:nu2:nu3:nu4 = 0.07:0.24:0.49:0.20, which is in good agreement with cold-wall, arrested-relaxation results. The vibrational energy distributions are nu1:nu2:nu3 = 0.79:0.19:0.02 for GeH4,nu1:nu2:nu3 = 0.54:0.43:0.03 for PH3, nu1:nu2:nu3:nu4 = 0.20:0.48:0.22:0.10 for PD3, nu1:nu2 = 0.75:0.25 for HBr, and nu1:nu2:nu3 = 0.33:0.55:0.12 for DBr. The Cl + GeH4 and PH3 reactions are approximately two times faster than Cl + HI. Einstein coefficients for a range of vibrational-rotational levels of HCl, HF, DCl, and DF are presented in the Appendix