Formal Interpretation of the Compensation Phenomenon

If Et and E are significantly differing the resultant Arrhenius plot will obviously be curved (of., Hulett, 1964), but for a 50°C wide temperature interval (including room temperature), the deviation from linearity is not significant if E — Ei =5 kcal mole-1. 

Some Types of Correlation Between Arrhenius Parameters as a Result of Varying Individual Parameters in Equation (46)a 

Variables in No. equation [26] Restricting conditions Type of correlation between A and E 

The assumption on two distinct reaction paths expressed by equation (46) is a simplification of most real cases. Attempts have been made to examine Arrhenius parameters of reactions proceeding not on two discrete energy levels but in a continuous energy interval. According to preliminary results (Mayer, unpublished), compensation trends similar to those of Table 8 are to be expected if the paths of significantly different energies make an appreciable contribution to the total rate. 

As for physical reasons of the above assumption, the following possibilities could be considered (Simonyi and Tiidos, to be published)  

---