Infrared Multiphoton Decomposition of 1-Chloro-1-fluoroethene

Article abstract of DOI:10.1246/bcsj.58.1358

Unimolecular dissociation and subsequent reactions of CH2=CFCl subjected to the infrared multiphoton excitation were studied with a focused geometry using the P(10) line of the 10.6 μm CO2 band at 952.9 cm^-1.The final products of the photolysis observed were CH=CCl, CH=CF, CH=CH, CH2CHF, and CH2=CF2.A series of diagnostic experiments shows that the primary processes of photolysis involve the molecular elimation of HF and HCl, to minor extend C-Cl bond rupture.The relative importance of the primary steps is tentatively estimated to be approximately 100:65:25, respectively.Primarily formed CH=CCl and CH=CF suffer from secondary photolysis absorbing additional photons.More fraction of CH=CF primary yield is decomposed than that of CH=CCl, due to the accidental resonance with the laser excitation line.CH=CH and CH2=CHF are concluded to be formed by the H atom abstraction reaction of CH2=C. and CH=CF. radicals generated during the photolysis respectively, CH2=CF2 beging formed by the recombination reaction between CH2=CF. radical and F atom.In the shock tube pyrolysis the formation of CH=CF predominates over that of CH=CCl.A mechanistic change to form CH=CF in the shock tube pyrolysis is suggested.