AbstractThe horizontal flame‐spreading behavior of slabs of uninhibited polypropylene (PP) and commercial polymethylmethacrylate (PMMA) is described, and the flame spread and mass vaporization rates are discussed. The quantities of peroxide and carbonyl moieties formed on the surface of PP beneath the flame front, determined by an iodometric procedure and by reaction with 2,4‐dinitrophenylhydrazine, are presented. A statistical analysis was performed to ascertain the significance of these quantities formed in four combustion environments, each differing in oxygen concentration. Flame and surface temperatures of the PP samples at each oxygen concentration as well as flame and surface temperatures of samples burned in 23% oxygen with an added external radiant heat source are presented. The data support the concept that surface oxidative reactions occur in the combustion of PP, that the quantity of oxidative products is related to the concentration of oxygen in the combustion environment, and the possible importance of these reactions in producing heat to propagate the flame is indicated. Comparison of PP and PMMA show that the two are quite dissimilar in flame‐spreading behavior.