The combustion of coal is responsible for nearly 40% of the world's electricity production, and char combustion accounts for about half of that amount. Clearly, an understanding of the combustion mechanism of carbon is of great importance not only because of its industrial significance but because it is a model heterogeneous reaction. A number of recent studies have been concerned with ab initio molecular orbital calculations on graphite including model chemistry and the reactions with molecular oxygen. This study is concerned with oxidation steps involving the attachment of oxygen to a graphene layer at high temperature leading to the formation of carbon monoxide, and particular attention is paid to the subsequent oxidation reactions. In addition, the reaction of oxygen with carbon catalyzed by metals inherent within the char matrix and the reaction of molecular oxygen with the analogous biomass char are investigated and their reaction paths are discussed.