The reactions of nitrogen atoms with butenes.

• Main Author: Gesser, Hymen.
• Other Authors: Winkler, C. (Supervisor)
• Format: Others
• Language: en
• Published: McGill University 1952
• Subjects: Chemistry.
• Online Access: http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=123998

It is becoming increasingly apparent that many reactions involve certain fundamental transformations that remain the same regardless of the overall process that occurs. These simple steps, or elementary reactions, generally involve free atoms or radicals. The existence of free radicals was first demonstrated by Gomberg (1) in 1900 in his classical identification of the triphenylmethyl radical in solutions of hexaphenylethane. In 1925, Taylor (2) suggested that simple radicals auch as the etbyl radical, C2H5, could be responsible for the observed high yields of ethane when ethylene and hydrogen mixtures were caused to react by mercury-photosensitization. It was first shown by Paneth and Hofeditz (3) that free radicals could be detected by their reaction with a metallic mirror deposited on the walls of a tube through which a carrier gas, together with the radicals, was flowing. The half-life ot the methyl radicals was shown to be about 0.006 sec., a value which was considered to be quite appreciable for a free radical. Rice and co-workers (4) soon obtained evidence to indicate that such free radicals were found during the thermal decomposition of hydrocarbons, and suggested that the majority of organic substances decomposed by a free radical mechanism. However it was still necassary to account for the fact that most organic decomposition reactions followed a first-order rate law, and that the experimental activation energies were usually smaller than the strength [...]