Photolysis of halogens in presence of trifluoroacetaldehyde. Some reactions of the trifluoroacetyl radical
- 1 January 1967
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Transactions of the Faraday Society
- Vol. 63, 80-90
- https://doi.org/10.1039/tf9676300080
Abstract
When a halogen X2 is photolyzed in the presence of CF3CHO in the vapour phase, the products are CO, CF3X, CF3COX and HX, provided that X2= Br2 or Cl2. Quantitative analyses of the products in the range 25–250°C indicate that the overall reactions are [graphic omitted] These are most readily explained by the reactions, X+CF3CHO →HX+CF3CO CF3CO+X2→CF3COX+X (6) CF3CO →CF3+CO. (7) Assuming that this mechanism is correct, we obtain, k7/k6,Br2 =(11.4 ± 3.0)× 10–3 exp [–(8,800 ± 200)/RT], k7/k6,Cl2 =(6.3 ± 0.8)× 10–3 exp [–(6,500 ± 100)/RT], mole cm–3. It is estimated that E7 10 kcal mole–1 and A7⩽2.6×1010 sec–1. Comparisons are made of the reactivities of CF3CO and CF3 radicals and of the stabilities of the CF3CO and CH3CO radicals. The relevance of the results to the primary act in the photolysis of hexafluoroacetone is discussed. No reaction occurred between CF3CHO and I2 under a variety of conditions.Keywords
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