ESR Studies of γ-Irradiated η-Octadecyl Disulfide

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Abstract
Octadecyl disulfide irradiated at — 196°C in the absence of oxygen exhibits radicals reflecting breakage at the sulfur group to form RS·radicals as well as breakage in the alkyl group. During storage of the samples at from 0° to 40°C an increase in RS·concentration is observed while reduction of radicals in the alkyl group takes place. After initial rapid reactions occurring immediately after warm‐up, a lower rate is observed for the increase in RS·content and decay of the radicals associated with the alkyl group. Both of these slower processes appear to occur as a result of a common reaction with an activation energy of about 13 kcal/mole. It is believed that this reaction involves the combination of a disulfide link with a radical in the alkyl group and occurs as a result of molecular diffusion in the crystalline material. Calculations based on a diffusion model yield theoretical curves which can be made to fit the experimental results within the limits of experimental error.