Energy transfer in thermal methyl isocyanide isomerization. Relative cross sections of fluoroalkanes and nitriles

The inert gas effect on the thermal isomerization of methyl isocyanide at 280.5° by the members of the homologous series of n-perfluoroalkanes and n-nitriles has been studied up to C6 in both cases. Relative collision diameters of these molecules, appropriate for the phenomenon of vibrational energy transfer involved, were obtained. ΔσCF2 = 0.54 Å is close to the value for ΔσCH2; higher perfluoroalkanes and alkanes are closely comparable in effective size. A dipolar orientation effect on the collision diameter of nitriles was observed. Some corrections and additions to earlier published values for hydrocarbons are described.

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Author Leonard D. Spicer Radiology