Abstract
The light-induced addition of SF5Cl to ethylene (E) has been studied in a series of gas-phase experiments in which concentration, relative light intensity and temperature have been varied. The results can be rationalized by the following chain mechanism in which the addition step (2) is appreciably reversible in the temperature range studied: SF5Cl +hv → SF5·+ Cl·(1) SF5·+ E ⇌ SF5E·(2), (–2) SF3E·+ SF5Cl → SF5ECl + SF5·(3) Cl·+ E → ECl·(4) ECl·+ SF5Cl → ECl2+SF5·(5) SF5·+ SF5·→ S2F10(6) From a series of experiments in which both pressure and temperature were varied the following rate expressions were obtained. k2/k½6=(3.9 ± 0.6) exp (–1,900 ± 200/RT)1.½mole–½ sec–½,‡k–2/k3=(118 ± 20) exp (–6,660 ± 300/RT)1.–1 mole.
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