Hydrogen Chloride Vibrational Populations Produced by the H and D Atom Reactions with SCl2 and S2Cl2

Infrared emission intensities from HCl and DCl products in high vibrational levels have been used to measure energy partitioning in the reactions of H and D atoms with SCl₂ and S₂Cl₂. The results are compared to the infrared chemiluminescence from the H and D atom reactions with Cl₂. The relative vibrational level populations were measured under experimental conditions such that vibrational relaxation was minimized. The H atom reactions with SCl₂ and S₂Cl₂ partitioned >37% and >36% of the available energy into vibrational energy of the hydrogen chloride product. Within our experimental error the fraction of energy partitioned to vibration was the same for the H and D atom reactions. In the reactions of H and D with SCl₂ and S₂Cl₂ the distribution of rate constants for formation of HCl^† and DCl^† into the vibrational levels apparently peaks at levels intermediate between $\text{υ\hspace{0.17em}=\hspace{0.17em}0}$ and the maximum possible level of vibrational excitation. The distributions are similar to those from the H and D atom reactions with Cl₂. The additional internal degrees of freedom in S₂Cl₂ relative to SCl₂ did not greatly affect the partitioning of energy to the HCl^† product.