Measurement of the Rate Parameters for Reaction of O(2³P) with Carbon Disulphide and Olefines, by Flash Spectroscopy

Abstract

THIS communication reports the measurement of the rate parameters for some reactions of O(2³P) by a new application of flash spectroscopy, which could be adapted to a wide range of fast reactions. The intermediate, the reactions of which are under investigation, is directly produced by the photolytic flash; the method requires the selection of a substance which reacts with the intermediate to produce a molecule which has intense light absorption at a wavelength suitable for kinetic spectroscopy. The reaction rate is determined by observing the rate of formation of this product, and the relative rates of competing reactions with added compounds can be measured by observing the diminishing yield of the “marker”. The rate of a reaction, in which neither reactants nor products exhibit convenient absorption spectra, can then be determined by the spectroscopic technique. In this investigation carbon monosulphide was produced by reaction of atomic oxygen with carbon disulphide and served as an ideal spectroscopic marker, because it possesses an intense band system at about 2600 Å and because its lifetime is very long compared with the time in which measurements need to be made.