Observed kinetic regularities and characteristics of detailed mechanisms

6 OBSERVED KINETIC REGULARITIES AND CHARACTERISTICS OF DETAILED MECHANISMS 

The analysis of observed kinetic parameters, primarily of the observed reaction rate order, and observed activation energy is an integral part of the kinetic study of complex catalytic reactions. 

In accordance with ref. 35, the terms observed order and observed activation energy can be used correctly only for power kinetic relationships. Here we will examine the relationships between the experimentally observed values dlnWfdlnA and d nW/d(— 1/RT) and the characteristics of the detailed mechanism. We believe these relationships to be rather informative. As the subject of the analysis we will take a one-route catalytic reaction with a mechanism that is linear with respect to the intermediates. 

Since the steps of these mechanisms usually involve the participation of no more than one molecule of the observed substance, the steady-state rate of its concentration variation will be presented as WA — pW, where p is the number of steps involving the substance participation of A and W the steady-state rate for any step (rate over the route). 

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