Infrared Chemiluminescence Studies of Cl + Hi, HBr, DBr, PH3, PD3, and GeH4: Vibrational Energy Disposal and Rate Constants

Article abstract of DOI:10.1021/j100224a017

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 the 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 ν1:ν2:ν3:ν4 = 0.07:0.24:0.49:0.20, which is in good agreement with cold-wall, arrested-relaxation results.The vibrational energy distributions are ν1:ν2:ν3 = 0.79:0.19:0.02 for GeH4, ν1:ν2:ν3 = 0.54:0.43:0.03 for PH3, ν1:ν2:ν3:ν4 = ).20:0.48:0.22:0.10 for PD3, ν1:ν2 = 0.75:0.25 for HBr, and ν1:ν2:ν3: = 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.