Ionization potentials free radicals forming

Even in reactions involving excited states or in reactions between two radicals, the primary interaction which determines the reactivity is thought to proceed adiabatically. The probability of nonadiabatic charge transfer also may not be ignored between a molecular specie with small ionization potential and a specie with large electron affinity, in particular in the form of free, gaseous, or nonsolvated state. In that... 

It is important to pay attention to the potential role of peroxides created on the surface of plasma-treated, including plasma polymer-coated, TPOs in the formation of durable bonds between the substrate and primer. It has been known for decades that the peroxides formed on the irradiated polymers (by y-ray. X-ray, electron beams, etc.) can be utilized in graft copolymerization of various monomers. This method is known as the peroxide method of radiation copolymerization [27]. The trunk polymer is first irradiated by ionizing radiation in a vacuum or in an inert gas environment. The irradiated polymer is exposed to air or oxygen to convert free radicals to peroxides. Thus created peroxides-containing polymers were used as the initiator of the free radical polymerization of the second monomer. The polymer peroxides are decomposed by heat or by the use of reduction/oxidation accelerator, i.e., peroxides are converted to free radicals. 

The energy of the 1236 A light is greater than the ionization potential of benzene, and hence additional reaction paths are available. All the above products were observed for the photolysis of benzene at 1236 A, with all except hydrogen having somewhat lower quantum yields. No pressure effect was observed in the photolysis at 1236 A. For the photolysis with either lamp, the addition of 3 torr NO to 1 torr of benzene eliminated allene, cyclohexadienes, biphenyl and dihydrobiphenyl as products, while the other products remained unaffected. Hentz and Rzad conclude that the former are formed by free-radical reactions, while the latter are formed by molecular elimination. In view of the curious pressure effects observed by Shindo and Lipsky at 1849 A, conclusions regarding the effect of added gases must be made with caution. 

Bond dissociation energies have already shown (Sec. 3.24) that the amount of energy required to form free radicals from alkanes decreases in the same order CH3 > r > 2° > 3°. If we combine these two sets of data—ionization potentials and bond dissociation energies—we see (Fig. 5.9) that, relative to the various alkanes concerned, the order of stability of carbonium ions is ... 

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