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The oxidation of CFClCFCl and CF 2 CCl 2
Author(s) -
Sanhueza Eugenio,
Heicklen Julian
Publication year - 1975
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.550070308
Subject(s) - chemistry , quantum yield , chlorine , yield (engineering) , chlorine atom , chain reaction , atom (system on chip) , reaction mechanism , photochemistry , medicinal chemistry , catalysis , organic chemistry , thermodynamics , physics , quantum mechanics , computer science , fluorescence , embedded system
The oxidation of CFClCFCl and CF 2 CCl 2 were studied at room temperature by chlorine‐ and oxygen‐atom initiation. The chlorine‐atom initiated oxidation of CFClCFCl yields CCl 2 FCF(O) as the exclusive product. Its quantum yield is ∼420, which gives k 3a / k 3b =210 where reactions (3a) and (3b) areThe O( 3 P )CFClCFCl reaction gives CClFO with a quantum yield of 0.80, polymer, and small amounts of an unidentified product which is probably cyclo‐(CFCl) 3 . Thereaction paths arewith k 9a / k 9 =0.80. The overall reaction of O( 3 P ) with CFClCFCl proceed one fifth as fast as the O( 3 P )‐C 2 F 4 reaction. When O 2 is also present, the same free‐radical chain oxidation occurs by O( 3 P )initiation as by chlorine‐atom initiation. The chlorine‐atom initiated oxidation of CF 2 CCl 2 gives CF 2 ClCCl(O) as the major product, with quantum yields ranging from 42 to 85. Smaller amounts of CF 2 O and CCl 2 O are produced in equal amounts with quantum yields of ∼3.5. The reactions responsible for the products areThe O( 3 P )‐CF 2 CCl 2 interaction yields CF 2 O andwith quantum yields of 1.0 and ∼0.85, respectively. In thepresence of O 2 the radical chain products are observed, but the mechanism is different than that for other chloroolefins.