The Cl2 photosensitized decomposition of O3: the reactions of ClO and OClO with O3

The temperature dependence of the bimolecular channels of the ClO + ClO reaction over the range T = 298–323 K

“…However it is still possible to estimate values for the branching ratios based on k 1b and k 1d from the present work by making assumptions on the value of k 1c . The studies by Burrows and Cox [26], Simon et al [18], and Nickolaisen et al [3] are in good agreement with regards to the value of k 1c and their findings average to k 1c = (7.5 ± 0.5) × 10 These values confirm channel (1d) as the minor reaction pathway of the ClO + ClO bimolecular channels but indicate that channel (1b) is the major contributor to the bimolecular decay, in disagreement with the studies by Wongdontri-Stuper et al [16] and Horowitz et al [19,20] which reported channel (1c) as the most efficient channel. The branching ratios from Cox and Derwent [15] are in good agreement with the estimate based on the rate constant from the present study although the absolute rate constants determined by Cox and Derwent are about a factor of two smaller than those obtained in this study.…”

“…A coeval study of the chlorine photosensitized decomposition of ozone by Wongdontri-Stuper et al [16] agreed with the mechanism identified by Cox and Derwent but obtained somewhat different branching ratios (1b) = 0.34, (1c) = 0.63, (1d) = 0.032 at T = 296 K.…”

“…Previous studies by Wongdontri-Stuper et al [16] and Horowitz et al [19,20] monitored the chlorine photosensitized decomposition of ozone, which allowed the determination of the branching ratios for channels (1b)-(1d) without characterizing the absolute rate constants. It follows that a direct comparison between the results of these studies and those from the present work is not possible as the masking of channel (1c) achieved in our laser photolysis study ruled out the possibility of determining the total k bi and, consequently, the branching ratios.…”

Environmental effects of large igneous province magmatism: a Siberian perspective

“…O 3 + OClO. The recommended value is based on results over the temperature range 262-296 K reported by Wongdontri-Stuper et al [1483]. Within the indicated uncertainty limits it also encompasses the somewhat lower room temperature result of Birks et al [146].…”

“…However, the value for E/R derived by these authors is only slightly lower than that estimated. (Table: 06-2, Note: 06-2) Back to [380] and Wongdontri-Stuper et al [1483], the Arrhenius parameters for k 2 were estimated. (Table: 92 Table F110.…”