Comparisons of energy disposal by the reactions of H atoms with Cl2, SCl2, S2Cl2 and SO2Cl2 from observation of HC1 infrared chemiluminescence

✍ Scribed by J.P. Sung; D.W. Setser

• Publisher: Elsevier Science
• Year: 1978
• Tongue: English
• Weight: 560 KB
• Volume: 58
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(78)80325-x

✦ Synopsis

Arrested rekxation infrared chemiluminescence studies of the H + Cl,, SCl2, !5&12, SCQ and SO&l2 reactions have been made. ihe mean fraction of vibrational fi a~ational) enem released to HCl is 0.40(0.10); 0.40(0.13); 0.38(?0.02); 0.33(?0.02) and 036 (20.02) for the series. Only the H + SC12 reaction shows a two component initial rotational distribution. The larger Cfv> and <fR) from H + SCl2, relative to the other polyatomic reagents, is consistent with the observation that this is the only reaction that shows forward scattering. The room temperature rate constanS a!so were measured, relative to H +Q2, and were found to decline in the series from 0.68 for Xi2 to 0.02 for SO2CI2. AU of thF_data supporX the suggestion (fit made by Heydtmann and Polanyi) that the unusual rotational energy disposal pattern from H + SC& h a consequence of migration of H from the initially encountered Cl to the second Cl, which then forms the HQ product; this pathway augments the direct reactive pathway, which gives HCI in lower f states.