GENERAL-SOLUTION FOR THE BASIC AUTOXIDATION SCHEME

The basic autoxidation scheme (BAS), first used by Bolland and Bateman, has been widely applied to oxidation studies for almost 50 years. Steady-state kinetic analysis of this reaction scheme has always depended upon making the simplifying assumptions of long kinetic chain length and/or a specific ratio of termination rate constants. We present and discuss a generalized steady-state kinetic solution to the BAS that is derived without any simplifying assumptions. We also combine this generalized solution with diffusion expressions to derive theoretical oxidation profiles appropriate to diffusion-limited oxidation situations. The modeling predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions yielding some unusual profile shapes.