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Vacuum ultraviolet (147 nm) photolysis of 1,2‐fluorochloroethane
Author(s) -
Ichimura T.,
Kirk A. W.,
TschuikowRoux E.
Publication year - 1977
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.550090505
Subject(s) - chemistry , halogen , acetylene , photochemistry , photodissociation , excited state , vinyl chloride , torr , ethylene , ultraviolet , chloride , quantum yield , organic chemistry , atomic physics , fluorescence , catalysis , alkyl , physics , quantum mechanics , copolymer , thermodynamics , polymer
1,2‐Fluorochloroethane was photolyzed at 147 nm in the pressure range of 3.8–20.9 torr. The effects of added NO, H 2 S, and large pressures of CF 4 were also investigated. The exponential extinction coefficient at 147 nm and 296°K was found to be 147 ± 4 atm −1 · cm −1 . The photochemistry in some respects is similar to that of ethyl chloride. The primary processes again appear to involve at least two excited states. One of these yields ethylene by FCl elimination (Φ ≃ 0.3) and has a lifetime of ∼3.2 × 10 −10 sec, with respect to an internal conversion to the vibrationally excited ground state or, more probably, a collisionally induced crossover to a state decomposing mainly by carbonhalogen bond fission. The molecular elimination of HCl, H 2 , and small amounts of HF also occurs but not apparently from the same state as does FCl. The quantum yields of products with radical precursors, however, are not large, and hence little, if any, of the FCl and probably none of HCl, H 2 , and HF subsequently dissociates. The vinyl fluoride and vinyl chloride, accompanying the elimination of HF and HCl, are postulated as possible sources of the secondary production of acetylene.