Relative Rates of Addition of Hydrogen Atoms to Olefines

Abstract

Hydrogen atoms were produced by the mercury‐photosensitized decomposition of n‐butane at 435±5 mm pressure and at 23.5±1°C. By introducing known amounts of olefine, the rate of addition of hydrogen atoms to the olefine could be measured relative to the rate of abstraction from the n‐butane by observing the fall in the rate of production of hydrogen. In this way, relative rates of addition to eight olefines were obtained, and the logarithms of the relative rate constants were found to correlate reasonably well with the atom localization energies of the olefines, but not with their maximum free valence.