Laser-induced addition of hydrogen fluoride to unsaturated molecules: the HF + CH2CF2 system

Abstract

Although certain classes of reactions are known to occur via 4-centre transition states, there has been no irrefutable proof that in the gas phase addition reactions also proceed via a 4-centre concerted process. Results of recent information theory calculations on the HF(υ) + CH2CF2 system indicate that it should be possible to observe reaction products for HF(υ = 5). Results are presented here on experiments attempting to achieve laser-induced 4-centre addition of HF to several unsaturated molecules (C2H2, C2H4, C4H6, CH2CF2, and CF2CClF). A mixture of HF and co-reactant was irradiated by a dye-laser tuned photo-acoustically to the fifth vibrational level of HF, and the resulting mixture was analysed by gas chromatography and mass spectrometry. There was no evidence of any laser-induced products. An upper bound was deduced for the HF + CH2CF2 addition rate constant at 610 K: [Formula: see text].