Decomposition of the permanganate/oxalic acid overall reaction to elementary steps based on integer programming theory

A systematic method to obtain chemically acceptable decompositions of the overall autocatalytic reaction permanagate/oxalic acid into elementary steps is presented. The decomposition process was based on integer programming theory and chemical evidence, and it can be applied to elucidate other mechanisms as well. As a result, we obtained mathematical justifications of the well-known autocatalytic nature and of the less-known crucial role of radical CO2. By inspecting the obtained decompositions, one can find reaction steps inaccessible to chemical intuition, and these point out the direction of further experimental investigations.