On the Apparent Compensation Effect Found for Two Consecutive Reactions

A critical analysis of the use of an overall single rate reaction equation instead of the true rate equation corresponding to a complex process consisting in two consecutive reactions is presented. In accordance with this approximation, often used in the kinetic analysis of the system in which several reactions take place, the overall process is described by the apparent activation parameters (the apparent activation energy, E _ap, and the apparent pre-exponential factor, A _ap) and the apparent conversion function. The theoretical isotherms (α=α(t), where a is the conversion degree and t is the time) have been simulated for a system in which two consecutive reactions occur. In this case, the apparent activation parameters depends on: (a) the considered range of the temperature; (b) the temperature, for a given conversion degree. It is shown that the apparent activation parameters are corrrelated by the compensation effect relationship: lnA _ap=α*+β*E _ap where α* and β* are the parameters of the linear regression. The possibility of using the apparent kinetic parameters to predict the isotherms α=α(t) for temperatures lower than those for which these parameters were evaluated, is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.