遅い熱異性化反応における溶媒粘度効果

抄録

This article presents the results of high - pressure kinetic study of slow thermal isomerizations (eq. 1) in viscous solvents. The results clearly demonstrated that the analysis based on the transition state theory (TST) becomes invalid only under extremely viscous conditions. By in - serting the observed rate constants and the extrapolated TST - expected rate constants to eq. 2, diffusion - limited rate constants kdif were estimated. The values thus obtained gave linear Ar - rhenius plots suggesting the present reactions proceed via two - step mechanism, namely, a dif - fusion - limited rate process followed by an activation - limited one.