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The dynamics of formation of vibrationally excited HF in reactions of O (2 1 D 2 ) atoms with partially fluorinated alkanes
Author(s) -
Burks T. L.,
Lin M. C.
Publication year - 1981
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550130918
Subject(s) - chemistry , excited state , exothermic reaction , oxygen , chemical reaction , photochemistry , atomic physics , organic chemistry , physics
The nascent vibrational energy distributions of the HF† formed in the reactions of a series of partially fluorinated alkanes (R F H; R F = CH 2 F, CHF 2 , CF 3 , C 2 F 5 , C 3 F 7 , and C 7 F 15 ) with electronically excited oxygen atoms O(2 1 D 2 ) have been determined by measuring the appearance times of stimulated emissions from various vibration–rotation transitions in a grating‐tuned optical cavity. The vibrational energy contents of the HF formed in these reactions were found to be considerably greater than statistically expected. These reactions are believed to occur via vibrationally excited short‐lived α;‐fluorinated alcohols (R F OH†), formed by insertion of the O(2 1 D 2 ) atoms into CH bonds. The observation of nonstatistical energy partitioning in the above reactions is in clear contrast to the result obtained from the O(2 1 D 2 ) + CF 3 CH 3 reaction that produces the β‐fluorinated alcohol CF 3 CH 2 OH, from which the HF product carries a near statistical vibrational energy distribution. A mechanism for HF† formation in these very exothermic reactions is presented.