DETERMINATION OF PRODUCT BRANCHING RATIO OF THE CLO SELF-REACTION AT 298-K

The Cl2-sensitized continuous photolysis of O3 mixtures in O2 was inve stigated at 298 K using time resolved single wavelength and diode arra y spectroscopy to monitor the decay of O3 and the formation of OClO. P HI(-O3) was found to be 4.1 +/- 0.4. This value, combined with the det ermination of the initial rates of OClO formation, allowed the evaluat ion of the following branching ratios into the three bimolecular dispr oportionation channels of ClO reactions; k3a/k3 = 0.40 +/- 0.08, k3b/k 3 - 0.42 +/- 0.08 and k3c/k3 - 0.18 +/- 0.02 where ClO + ClO --> Cl2 O2 (3a), ClO + ClO --> Cl + Cl + O2 (3b) and ClO + ClO --> Cl + OClO (3c).