Kinetics and thermochemistry of the equilibrium CCl sub 3 + O sub 2 r reversible CCl sub 3 O sub 2
- Catholic Univ. of America, Washington, DC (USA)
- Universite de Bordeaux, Talence (France)
- Sandia National Lab., Livermore, CA (USA)
- Illinois Institute of Technology, Chicago (USA)
The equilibrium CCl{sub 3} + O{sub 2} {r reversible} CCl{sub 3}O{sub 2} has been studied experimentally between 351 and 461 K, the temperature range in which it could be clearly observed and characterized. Equilibrium constants were measured as a function of temperature at two laboratories using different techniques and different experimental conditions. In both investigations, CCl{sub 3} was produced by pulsed UV photolysis, and CCl{sub 3} relaxation to equilibrium, in the presence of O{sub 2}, was monitored in time-resolved experiments, using either photoionization mass spectrometry or UV absorption spectrometry. The results indicate a considerable weakening of the CH{sub 3}-O{sub 2} bond caused by chlorine substitution on the CH{sub 3} group, from 32.4 kcal mol{sup {minus}1} (DH{degree}{sub 298}(CH{sub 3}-O{sub 2})) to 19.9 kcal mol{sup {minus}1} (DH{degree}{sub 298}(CCl{sub 3}-O{sub 2})).
- OSTI ID:
- 6898987
- Journal Information:
- Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:8; ISSN 0022-3654; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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