While a reaction may exhibit one set of kinetic behavior at early conversion, that behavior may change due to:
* changes in catalyst resting state influenced by changing substrate concentrations
* multiple or changing mechanisms influenced by substrate or product concentrations
* catalyst activation (an initiation period)
* product inhibition
* irreversible (or reversible) catalyst death
In the case of saturation kinetics described above, provided that [A] is not present in a large excess relative to [B], saturation conditions will only apply at the beginning of the reaction. As the substrate is consumed, the concentration decreases and eventually [A] is no longer sufficient to completely overwhelm [Cat]. This is manifested by a gradual change in rate from 0-order to some higher (i.e. 1st, 2nd, etc.) order in [A]. This can also be described as a change in catalyst resting state from the bound form to the unbound form over the course of the reaction.
In addition to simply slowing the reaction, a change in catalyst resting state over the course of the reaction may result in competing paths or processes. Multiple mechanisms may be present to access the product, in which case the order in catalyst or substrate may change depending on the conditions or point in the reaction. A particularly useful probe for changes in reaction mechanism involves examination of the normalized reaction rate vs. catalyst loading at multiple, fixed conversion points. Note that the normalized reaction rate:
:k = 
adjusts for the consumption of substrate over the course of the reaction, so only rate changes due to catalyst loading will be observed. A linear dependence on catalyst loading for a given conversion is indicative of a first order dependence on catalyst at that conversion, and one can similarly imagine the non-linear plots resulting from higher order dependence. Changes in the linearity or non-linearity from one set of conversion points to another are indicative of changes in the dependence on catalyst over the course of the reaction. Conversely, changes in the linearity or non-linearity of regions of the plot conserved over multiple conversion points (i.e. at 30, 50, and 70%) are indicative of a change in the dependence on catalyst based on the absolute catalyst concentration.
Catalyst interactions with multiple components of a reaction mixture can lead to a complex kinetic dependence. While off-cycle catalyst-substrate or catalyst-product interactions are generally considered "poisonous" to the system (certainly the case in the event of irreversible complexation) cases do exist in which the off-cycle species actually protects the catalyst from permanent deactivation.
In either case, it is often essential to understand the role of the catalyst resting state.