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. St eady-state kinetic analysis of this reaction scheme has always depende d 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 i s derived without any simplifying assumptions. We also combine this ge neralized solution with diffusion expressions to derive theoretical ox idation profiles appropriate to diffusion-limited oxidation situations . The modeling predicts conditions yielding unusual dependencies of th e oxidation rate on oxygen concentration and on initiation rate, as we ll as conditions yielding some unusual profile shapes.