The oxidation of cis- and trans-CHClCHCl

✍ Scribed by Eugenio Sanhueza; Julian Heicklen

• Publisher: John Wiley and Sons
• Year: 1975
• Tongue: English
• Weight: 580 KB
• Volume: 7
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550070409

✦ Synopsis

When C1 atoms react with CHClCHCl in the presence of 0 2 at 31°C, a long-chain oxidation occurs. The products are the geometrical isomer of the starting olefin and CHCIO, HCI, CO, and CC120. The quantum yields of the oxygen-containing products arethesamewithbothisomersandare*{CHClO] = 3O,@(CO) = 11.7,and +{CCI20) = 1.29.

The reaction then proceeds

The chlorine atom adds to the olefin and is followed by 0 2 addition.

with k,;,/kab = 19 and k,,/k7 -0.5, where k7 = k,, + klb. The CC12H radical oxidizes to regenerate the chain carrier.

O r 3 P ) reacts with CHClCHCl at 25°C with a rate coefficient of 6.6 X 108 M-' sec-I for trans-CHCICHCI and 2.8 X lo8 M-' sec-' for cis-CHCICHCI. The reaction channels are ( 1 4 O(3P) + CHClCHCl + CO + HCI + CClH (lb) + CH zClCCl(0) (lc) -+ CHClCHClO* with kl,/kl = 0.23 and 0.28, respectively, for the cis and trans compounds. Reaction (1 b) occurs < 4% of the time. Reaction (Ic) leads to polymer production and presumably, via redissociation, to the geometrical isomer of the starting olefin. I n the presence of 0 2 the same long-chain oxidation is observed as in the chlorine-atom initiated oxidation. The chain-initiating step is C H C l + 0 2 -HO + ClCO + C 1 + CO