Reactions of electronically excited iodine atoms I(52P½) with Cl2, Br2, ICl and IBr
- 1 January 1968
- journal article
- Published by Royal Society of Chemistry (RSC) in Transactions of the Faraday Society
- Vol. 64, 1228-1239
- https://doi.org/10.1039/tf9686401228
Abstract
Electronically excited iodine atoms, I(52P½), have been generated by the flash photolysis of CF3I. The excited atoms have been monitored by time-resolved absorption spectroscopy both in the ultra-violet and the vacuum ultra-violet, together with the products of their reactions with Cl2, Br2, ICl and IBr. The decay of I(52P½) in the presence of these gases is dominated by exothermic, metathetical reactions such as I(52P½)+ Cl2→ICl + Cl, where Cl2 and ICl are in their electronic ground states. The analogous reactions of I(52P3/2), are endothermic and do not contribute significantly under the experimental conditions. Collisionally induced spin orbit relaxation of I (52P½) into ground state atoms. I(52P3/2) with Cl 2, Br2 , ICl and IBr are 2.1 × 10–13, 1.5 × 10–12, 3.4 × 10 –12, and 4.3 × 10–12 cm3 molecule –1 sec–1, respectively. A comparison may be made with the rate constants for the analogous reactions of I(52P3/2) from data for the reverse reactions combined with equilibrium constants, calculated by statistical mechanics.Keywords
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